CN100446307C - Method for preparing lithium secondary cell electrode containing nano additive - Google Patents
Method for preparing lithium secondary cell electrode containing nano additive Download PDFInfo
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- CN100446307C CN100446307C CNB2005100865125A CN200510086512A CN100446307C CN 100446307 C CN100446307 C CN 100446307C CN B2005100865125 A CNB2005100865125 A CN B2005100865125A CN 200510086512 A CN200510086512 A CN 200510086512A CN 100446307 C CN100446307 C CN 100446307C
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Abstract
The invention is related to three methods for preparing poles of lithium secondary battery of containing Nano additive. First two methods include procedures: adding Nano material to raw material for coating positive poles or/and negative poles of lithium secondary battery; then, coating poles according to conventional method. The third method presses and embeds Nano material to conventional pole sheets prepared through coating procedure according to conventional method. The third method omits steps of surface modification/cladding process in current technique. Advantages are: simple technique, low cost, raised available capacity of material of positive material, circular stability and safety.
Description
Technical field
The invention belongs to the high-energy battery technical field, specifically relate to a kind of preparation method who contains the lithium secondary battery electrode of nanometer additive.
Background technology
The employed positive electrode active materials of lithium ion battery mainly comprises the LiCoO of rock salt structure at present
2And LiNiO
2, spinel structure LiMn
2O
4And the LiFePO of olivine structural
4Be under the condition of 4.2V with battery charge to current potential to lithium metal, LiCoO
2Actual capacity can reach about 150 MAH/grams spinelle LiMn
2O
4Actual capacity can accomplish about 120 MAH/grams the LiFePO of olivine structural
4Capacity can reach about 150 MAH/grams.In general, improve the utilized capacity that charging voltage can further improve material, but this will cause the heavy damage of material structure, and might bring potential safety hazard.
In above several electrode materials, because LiCoO
2Therefore stable performance is easy to synthesize, and is the earliest by business-like anode material for lithium-ion batteries, is widely used in now in the commodity low capacity lithium ion battery.But, because the reserves of Co in the earth's crust are lower, with LiCoO
2For the lithium ion battery of positive electrode is difficult to reduce production costs, thereby become the important restraining factors of high capacity lithium ion battery production and popularization.LiNiO
2Theoretical specific capacity and LiCoO
2Close, reality can utilize specific capacity to compare LiCoO
2Higher, production cost is relatively low.But, synthetic single-phase LiNiO
2Very big difficulty is arranged on technology, and LiNiO
2Structure and thermal safety all be not so good as LiCoO
2Stable, still be difficult at present promote the use of.Mn is abundant at the occurring in nature reserves, spinelle LiMn
2O
4The relative LiNiO of synthesis technique
2Also simple.But, when 55 ℃ or above temperature, because Mn
3+The stripping of ion and cause the destruction of material structure and specific capacity to reduce.The LiFePO of olivine structural
4It is emerging in recent years a kind of positive electrode.This material structure is stable and cheap.Though this conductivity of electrolyte materials is lower, after suitably doping and surface bag carbon were handled, its rate charge-discharge performance can be greatly improved.Once release, LiFePO
4Just receive people's very big concern, become one of the most popular in recent years positive electrode.Therefore, spinelle LiMn
2O
4With olivine LiFePO
4It is the positive electrode that is hopeful most to be applied in the lithium ion battery of new generation, particularly high capacity lithium ion battery.
Studies show that, by above-mentioned positive electrode active materials is used Li, Ni, Co, Mn, Mg, Ga, Ti, Fe, Al, Sn, Zr, Si, W, B etc. suitably mix or element substitution, can obtain the derived material identical with the fertile material structure.These derived materials have improved the structural stability of fertile material to a certain extent, or reduced production cost, but, reduced the theoretical specific capacity and the reality of electrode material and can utilize capacity with the derived material that the inactive element substitution electro-chemical activity of electrochemistry element obtains.
Obviously, existing positive electrode active materials can not satisfy the requirement of producing big capacity or powerful lithium secondary battery (lithium secondary battery is the general designation of lithium ion battery and serondary lithium battery).Improve the actual specific capacity of positive electrode and improve cyclicity, need the new positive electrode of exploitation or current material is carried out modification, to improve the chemical property of material.For the reason that capacitance of lithium secondary battery reduces, it is generally acknowledged that at present the factor relevant with positive electrode has: (1) under higher charging potential, electrolyte generation decomposition and consumption falls a part of lithium, and the specific capacity of material and the cycle performance of battery are reduced; (2) under higher charged state, have active transition metal ions in the positive electrode and leave material body, enter electrolyte, reduced the active component in the positive electrode, destroyed the structure of material; (3) lack the state of lithium in the positive electrode degree of depth, the transition metal ions tropic rearrangement in the positive electrode, the crystal structure generation irreversible transition of material reduces the electro-chemical activity of positive electrode; (4) at present the minor amount of water that contained of commodity electrolyte makes electrolyte be acid, and the positive electrode that is alkalescence is had corrosivity.
In the applicant's the ZL of Chinese patent formerly 01134448.2, disclose a kind ofly by the method that surface of positive electrode active material is coated or modification is handled, significantly improved the structural stability of positive electrode, effectively improved the performance of electrode material.Because the structural stability that has improved electrode material is handled in this surface modification/coating, therefore such electrode material can be charged to higher voltage, higher specific capacity is provided, and guarantees that simultaneously the cyclical stability of electrode material can variation.But above-mentioned surface modification/coating is handled after electrode active material is synthetic and is carried out, and it makes the preparation technology of electrode active material become complicated, has also increased the preparation cost of electrode material.
Summary of the invention
The objective of the invention is to save surface modification of the prior art/coating treatment process, reducing the preparation cost of lithium secondary battery electrode material, thereby provide a kind of technology reality simple, with low cost, that can improve positive electrode simultaneously can utilize capacity, cyclical stability and fail safe, contain the preparation method of the lithium secondary battery electrode of nanometer additive.
The objective of the invention is to realize by the following technical solutions:
The invention provides three kinds of preparation methods that contain the lithium secondary battery electrode of nanometer additive.Wherein preceding two kinds of methods coat electrode according to conventional method then for coating cathode plate for lithium secondary battery or/and in the raw material of negative pole, add nano material.The third is coated with in the conventional electrodes sheet made from conventional method for nano material is pressed to embed, and obtains the negative or positive electrode sheet after the drying.
First kind of preparation method who contains the lithium secondary battery electrode of nanometer additive provided by the invention comprises following step:
1) nano material, binding agent and conventional electrodes active material are mixed;
The addition of described nano material accounts for the electrode material total weight and (comprises all dry material of preparation respective electrode slurry, but do not comprise metal forming or the plastic film that carries electrode material.Down with) 10
-7～0.2 times, if that is: only use additive to improve the performance of anodal and entire cell in positive electrode, then the addition of nano material just accounts for 10 of positive electrode total weight
-7～0.2 times; If by using additive to improve the performance of anodal and entire cell in negative material, then the addition of nano material just accounts for 10 of negative material total weight
-7～0.2 times; If use additive simultaneously in anodal and negative material, then the addition of nano material accounts for 10 of positive electrode total weight in the positive pole
-7～0.2 times, the addition of nano material accounts for 10 of negative material total weight in the negative pole
-7～0.2 times;
Described nano material is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 1～5000 nanometer;
Described nano material as additive is one or more the mixture that is selected from following various types of materials:
I) metal or nonmetallic simple substance material comprise Li, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, lanthanide series metal, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi, Po, At, Ra, actinide metals;
Ii) above-mentioned metal or nonmetallic oxide or composite oxides, the preferred MgO of oxide, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, Y
2O
3, La
2O
3, Fe
2O
3, MnO
2, ZrO
2, ZnO, CeO
2The preferred LiCr of composite oxides
2O
4, LiAlO
2, LiCoO
2, LiNiO
2, LiMn
2O
4
The iii) salt of above-mentioned metal such as carbonate, phosphate, silicate, vanadate, meta-aluminate, halide, or nitrate, preferred Li
3PO
4, AlPO
4, Mg
3(PO
4)
2, Li
2CO
3, NaAlO
2, LiAlO
2, and Li
2ZrO
3
Iv) double salt, preferred LiAl (SO
4)
2Or LiMPO
4, wherein M is selected from Mg, Al, Fe, Co, Ni, Zr, Cr, Ti or V;
Described binding agent is that Kynoar (PVdF) is or/and polyacrylonitrile (PAN);
Described binding agent accounts for 0.001～0.2 times of electrode material total weight;
Described conventional electrodes active material accounts for 0.2～0.99 times of electrode material total weight;
2) in the mixture that step 1) obtains, add solvent,, make wherein binding agent dissolving, mixture form uniform sizing material, coat electrode, promptly can be used as electrode after drying, the roller process and use according to conventional method 30～200 ℃ of stirrings;
Described solvent is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture;
The weight of described solvent accounts for 0.2～1000 times (solvent can all be removed) of electrode material total weight in the dry run of electrode.
First kind of preparation method who contains the lithium secondary battery electrode of nanometer additive provided by the invention also is included in the mixture of step 1) and adds conductive additive;
Described conductive additive is for being selected from carbon black (CB), acetylene black, metal powder and the metallic fiber one or more mixture;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 5 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
Second kind of preparation method who contains the lithium secondary battery electrode of nanometer additive provided by the invention comprises following step:
1) above-mentioned nano material and conventional electrodes active material are mixed;
The addition of described nano material accounts for 10 of electrode material total weight
-7～0.2 times;
Described conventional electrodes active material accounts for 0.2～0.99 times of electrode material total weight;
2) at 30～200 ℃, binding agent and solvent are mixed with the solution of binding agent, the weight of binding agent accounts for 0.001～0.2 times of total solution weight in the solution;
Described binding agent is that Kynoar (PVdF) is or/and polyacrylonitrile (PAN);
Described solvent is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture;
The weight of described solvent accounts for 0.2～1000 times of electrode material total weight;
3) with step 2) in the binder solution that obtains join in the mixture of step 1), mix once more, the slurry of making coats electrode according to conventional method, promptly can be used as electrode after drying, the roller process and uses;
Described binding agent accounts for 0.001～0.2 times of electrode material total weight.
Second kind of preparation method who contains the lithium secondary battery electrode of nanometer additive provided by the invention also is included in the mixture of step 1) and adds conductive additive;
Described conductive additive is for being selected from carbon black (CB), acetylene black, metal powder and the metallic fiber one or more mixture;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 10 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
Second kind of preparation method who contains the lithium secondary battery electrode of nanometer additive provided by the invention also is included in and adds diluent in the step 3); Described diluent is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture; Addition is 0.1～1000 times of binder solution volume;
Adding diluent is in order to regulate the viscosity of slurry, its addition is decided with the relative scale of employed electrode material and additive and physical property (as granularity, porosity and density etc.) separately, is suitable for electrode with the viscosity of gained slurry and coats be as the criterion (diluent can all be removed) in the dry run of electrode.
Provided by the invention the third contains the preparation method of the lithium secondary battery electrode of nanometer additive, comprises following step:
1) electrode active material, binder solution and mixing diluents is even, coat electrode according to conventional method, make the conventional electrodes sheet through super-dry, roll-in then;
The weight of the binding agent in the described binder solution accounts for 0.001～0.2 times of total solution weight;
Described binding agent is that Kynoar (PVdF) is or/and polyacrylonitrile (PAN); Described solvent is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture;
Described diluent is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture;
The component of diluent and solvent can be the same or different;
Described diluent accounts for 0.2～100 times of electrode material total weight, can all remove in the dry run of electrode; Adding diluent is in order to regulate the viscosity of slurry, its addition is decided with the relative scale of employed electrode material and additive and physical property (as granularity, porosity and density etc.) separately, is suitable for electrode with the viscosity of gained slurry and coats and be as the criterion;
Described electrode active material accounts for 0.2～0.99 times of electrode material total weight;
2) aforesaid nano material is evenly mixed with dispersant, make suspension-turbid liquid, evenly coat on the electrode slice that step 1) makes, through obtaining the negative or positive electrode sheet after dry, the roll-in once more;
Described dispersant is for being selected from N-methyl pyrrolidone (NMP), acetone and the cyclopentanone one or more mixture;
The content of nano material accounts for 10 of suspension-turbid liquid total weight in the described suspension-turbid liquid
-6～0.2 times;
The addition of described nano material accounts for 10 of electrode material total weight
-7～0.2 times.
Provided by the invention the third contains the preparation method of the lithium secondary battery electrode of nanometer additive, also is included in the mixture of step 1) to add conductive additive;
Described conductive additive is for being selected from carbon black (CB), acetylene black, metal powder and the metallic fiber one or more mixture;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 10 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
In above-mentioned three kinds of methods the electrode slice of indication can metal forming or plastic film be carrier.When using metal forming as carrier, tinsel is electrode current collecting body; When using plastic film as carrier, need that the electrode slice on the plastic film is pressed on the wire netting rear and can be used as electrode and use, wire netting is collector.
To dress up lithium secondary battery according to the conventional method seal group with the lithium secondary battery electrode that contains nanometer additive of above-mentioned any method preparation, and inject electrolyte.The basic structure of this lithium secondary battery is: with the material that contains positive active material as positive pole, can store up lithium the material of lithium ion maybe can be provided be negative pole with various, with organic or inorganic electrolyte solution or polymer dielectric or solid electrolyte is electrolyte, be equipped with common barrier film in addition, collector, battery case and lead-in wire are formed.Have the first in above positive pole and the negative pole at least with method provided by the present invention preparation, promptly added described nano material in the electrode.Positive pole is burn-on respectively with an end of negative pole, and lead-in wire is back to link to each other with the battery case two ends or the electrode column of mutually insulated.
Described lithium secondary battery can use liquid electrolyte or polymer dielectric or gel electrolyte or solid electrolyte; Cell shapes can be made button (individual layer), cylindrical (multilaminate coiled), square multiple shape and specifications such as (multilayer foldings or multilaminate coiled) by above-mentioned basic structure.This lithium secondary battery has characteristics such as reversible capacity height, cyclicity are good, fail safe height, can be used as portable power source and be used for for example mobile phone, notebook computer, camera, video camera and other mobile electronic device and cordless power tool, and pure electric vehicle and hybrid-power electric vehicle (comprising electric bicycle, battery-operated motor cycle, electro-tricycle and electric automobile) etc., also can be used for the occasions such as energy-accumulating power station of various scales.
In lithium secondary battery, above-mentioned nano material can interact with electrolyte, engulf the harmful components that wherein may produce corrosiveness to electrode active material, generation helps to improve the cyclical stability of electrode material and the gas and the fluid molecule of thermal safety in the electrolyte of sealed cell, helps to improve the cyclical stability of electrode material and the solid product of thermal safety at positive pole or/and the particle surface of negative material produces simultaneously.The liquids and gases molecule that effect generates helps to generate protective layer at circulation time first in electrode material surface, suppresses the oxidation Decomposition of electrolyte; Be deposited on positive pole or/and the solid product on negative material surface itself is exactly a kind of solid electrolyte interface phase (SEI), the have metal or the nonmetallic ion that help by the nanometer additive stripping of this tunic move in the positive electrode active materials body, in positive electrode active materials, form a kind of surperficial solid solution, improve the structural stability of positive electrode and improve its thermal safety.Because the raising of positive electrode structural stability makes prepared in this way lithium secondary battery can be charged to higher voltage, and higher capacity can be provided, and shows better fail safe simultaneously.Therefore, use the electrode of the method for the invention preparation to have some other advantages that extremely do not possess as all advantages that electrode was had of active material with the material of nano surface modification/method for coating preparation.
The advantage of method provided by the invention is: 1) nano material as additive can directly join in other the electrode material, handles according to conventional method, coats electrode, does not need other operation, and technical process is simple; Also can add separately after making electrode being coated with conventional method, flexible; 2) the nanometer additive use amount is low, cheap and easy to get, increases the cost of manufacture of battery hardly; 3) this nanometer additive to cycle performance of battery and security performance to improve effect remarkable; 4) owing to use additive to improve the structural stability and the fail safe of active material, battery can be charged to higher voltage, even therefore the weight and the bulk factor of nanometer additive are taken into account, the actual specific capacity of battery still can be significantly increased, and has high cyclicity and and high security simultaneously.
Description of drawings
Fig. 1 be embodiment 05 preparation with commodity LiCoO
2Used Al in the positive electrode for active material
2O
3The charging and discharging curve of the lithium secondary battery of nanometer additive.
Fig. 2 be embodiment 05 preparation with commodity LiCoO
2Used Al in the positive electrode for active material
2O
3The cycle performance curve of the lithium secondary battery of nanometer additive.
Embodiment
Embodiment 01
According to first method, preparation contains the cathode plate for lithium secondary battery of metal A l additive.With average particle size is the metal A l particle of 1500 nanometers, the commodity positive electrode active materials LiCoO that average particle size is 4500 nanometers
2And binding agent Kynoar (PVdF) mixes.The addition of Al powder accounts for 10 of positive electrode total weight
-3Doubly, binding agent PVdF accounts for 0.05 of positive electrode total weight, positive electrode active materials LiCoO
2Account for 0.949 times of positive electrode total weight.
In said mixture, add solvent N-methyl pyrrolidone (NMP), the weight of solvent accounts for 5 times of positive electrode total weight, 60 ℃ of stirrings, make binding agent dissolving wherein, mixture forms uniform sizing material, coat electrode according to conventional method, promptly can be used as positive plate after drying (remove and desolvate), the roller process and use.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
With this positive plate is positive pole, with metal lithium sheet as negative pole (negative pole is excessive), with 1 mole of LiPF
6The mixed solvent (volume ratio 1: 1) that is dissolved in 1 liter of vinyl carbonate (EC) and dimethyl carbonate (DMC) uses the PP/PE barrier film of porous as electrolyte, is assembled into battery in the glove box of argon shield.After battery left standstill 4 hours, adopt Wuhan blue electricity (Land) cell tester that battery is carried out constant current (0.1 milliampere/square centimeter) and discharge and recharge.Discharge and recharge in cut-ff voltage such as the table 2 listed.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 02
According to first method, preparation contains the cathode plate for lithium secondary battery of simple substance Si nanometer additive.With granularity is that the simple substance Si particle of 800 nanometers, conductive agent carbon black, binding agent polyacrylonitrile (PAN) and the average particle size that average particle size is 60 nanometers are the commodity positive electrode active materials LiFePO of 5000 nanometers
4Mix.The addition of nanometer Si powder accounts for 10 of positive electrode total weight
-4Doubly, binding agent PAN accounts for 0.05 of positive electrode total weight, and the conductive agent carbon black accounts for 0.085 of positive electrode total weight, positive electrode active materials LiFePO
4Account for 0.865 times of positive electrode total weight.
In said mixture, add solvent N-methyl pyrrolidone (NMP), the weight of solvent accounts for 5 times of electrode material total weight, 60 ℃ of stirrings, make binding agent dissolving wherein, mixture forms uniform sizing material, coat electrode according to conventional method, promptly can be used as positive plate after drying (remove and desolvate), the roller process and use.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
Assemble Experimental cell and carry out the constant current charge-discharge circulation according to the method for embodiment 01.Discharge and recharge in cut-ff voltage such as the table 2 listed.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 03
According to second method, preparation contains the lithium secondary battery electrode of C nanometer additive.With average particle size is that the equal granularity of C powder peace of 200 nanometers is the commodity positive electrode active materials LiNi of 6000 nanometers
0.8Co
0.2O
2Mix; The acetone soln (concentration of PVdF is 0.2 grams per milliliter) of binding agent PVdF is joined in the above mixture, mix once more, make slurry at 60 ℃.Coat electrode according to conventional method, promptly can be used as anodal the use after drying, the roller process.The addition of C powder accounts for 10 of positive electrode total weight
-5Doubly, binding agent PVdF accounts for 0.05 of positive electrode total weight, positive electrode active materials LiNi
0.8Co
0.2O
2Account for 0.950 times of positive electrode total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
Be assembled into battery according to the method among the embodiment 01.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 04
According to second method, preparation contains the lithium secondary battery electrode of S nanometer additive.With average particle size is the commodity positive electrode active materials LiMn that the S nano material of 2000 nanometers, conductive agent carbon black that average particle size is 50 nanometers and average particle size are 4000 nanometers
2O
4Mix; The nmp solution (concentration of PAN is 0.2 grams per milliliter) of binding agent PAN is joined in the above mixture, mix once more, make slurry at 60 ℃.Coat electrode according to conventional method, promptly can be used as electrode after drying, the roller process and use.In the dry positive plate of making, the S additive accounts for 0.1 of electrode material total weight, and conductive agent accounts for 0.08 of electrode material total weight, and weight of binder accounts for 0.05 of electrode material total weight, active material LiMn
2O
4Account for 0.770 of electrode material total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
Be assembled into battery according to the method among the embodiment 01, the statistics loop-around data of positive active material is listed in table 2.
Embodiment 05
According to first method, be the Al of 50 nanometers with granularity
2O
3Nano particle, conductive agent carbon black, binding agent PVdF and the average particle size that granularity is 100 nanometers be the commodity positive electrode active materials LiCoO of 1000 nanometers
2Mix.Nanometer Al
2O
3The addition of powder accounts for 10 of positive electrode total weight
-6Doubly, binding agent PVdF accounts for 0.05 of electrode material total weight, and carbon black accounts for 0.08 times of positive electrode total weight, positive electrode active materials LiCoO
2Account for 0.870 times of electrode material total weight.
In said mixture, add solvent NMP, the weight of solvent accounts for 5 times of electrode material total weight, 60 ℃ of stirrings, make binding agent dissolving wherein, mixture forms uniform sizing material, the method that coats electrode according to routine coats electrode, promptly can be used as the anodal use of electrode slice after drying (remove and desolvate), the roller process.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of positive electrode active materials is listed in the table 2.
Be assembled into battery according to the method among the embodiment 01.The charging and discharging curve of this lithium secondary battery and cycle performance curve are respectively as depicted in figs. 1 and 2.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 06-09
According to the method among the embodiment 05, prepare a series of cathode plate for lithium secondary battery that contain the oxidate nano additive, it uses the kind and the consumption of conductive agent, binding agent and coordinative solvent and nanometer additive to list in the table 1, and the related data of positive electrode active materials is listed in the table 2.
Be assembled into battery according to the method among the embodiment 01.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 10
According to second method, be the La of 500 nanometers with average particle size
2O
3Nano material, average particle size are the conductive agent carbon black of 50 nanometers and the positive electrode active materials LiNi that average particle size is 4000 nanometers
0.4Co
0.2Mn
0.4O
2Mix; The cyclopentanone solution (concentration of PVdF is 0.2 grams per milliliter) of binding agent PVdF is joined in the above mixture, mix once more, make slurry at 60 ℃.Coat electrode according to conventional method, promptly can be used as positive plate after drying, the roller process and use.In the dry positive plate of making, La
2O
3Additive accounts for 10 of electrode material total weight
-4, conductive agent accounts for 0.08 of electrode material total weight, and binding agent accounts for 0.05 of electrode material total weight, positive active material LiNi
0.4Co
0.2Mn
0.4O
2Account for 0.870 of electrode material total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
According to the assembling of the method among the embodiment 01 simulated battery, the statistics loop-around data of positive active material is listed in table 2.
Embodiment 11-14
According to the method among the embodiment 10, prepare a series of cathode plate for lithium secondary battery that contain nanometer additive, it uses the kind and the consumption of conductive agent, binding agent and coordinative solvent and nanometer additive to list in the table 1, and the related data of electrode active material is listed in the table 2.
According to the method assembled battery among the embodiment 1.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 15
According to the third method, be the conductive agent carbon black of 200 nanometers, the commodity positive electrode active materials LiMn that average particle size is 4000 nanometers with average particle size
2O
4, binding agent PVdF cyclopentanone solution (concentration of PVdF is 0.2 grams per milliliter) and diluent cyclopentanone mix, coat electrode according to conventional method.After super-dry, roll-in, make conventional positive plate.With average particle size is 500 nano-TiOs
2Powder body material evenly mixes with the dispersant cyclopentanone, makes suspension-turbid liquid, evenly coats on the above conventional electrodes sheet that makes, through obtaining positive plate after drying, the roll-in once more.In the dry positive plate of making, TiO
2Additive accounts for 10 of electrode material total weight
-4, conductive agent accounts for 0.08 of electrode material total weight, and weight of binder accounts for 0.05 of electrode material total weight, positive active material LiMn
2O
4Account for 0.87 of electrode material total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
Be assembled into simulated battery according to the method among the embodiment 01, the statistics loop-around data of positive active material is listed in table 2.
Embodiment 16-19,
According to the method among the embodiment 15, prepare a series of cathode plate for lithium secondary battery that contain nanometer additive.Main difference between each embodiment is added nanometer additive kind difference.According to the heterogeneity of additive and conductive agent and positive electrode active materials, their content is separately adjusted to some extent.The kind of employed conductive agent, binding agent and coordinative solvent and nanometer additive and consumption are listed in the table 1 among each embodiment, and the related data of electrode active material is listed in the table 2.
Be assembled into battery according to the method among the embodiment 01.The statistics loop-around data of positive active material is listed in table 2.
According to the method for embodiment 05, be the LiAl (SO of 2000 nanometers with average particle size
4)
2Nanometer additive, average particle size be conductive agent carbon black and binding agent PVdF and the average particle size of 50 nanometers be 6000 nanometers in the middle of mutually charcoal bead (MCS) negative material evenly mix, add an amount of solvent cyclopentanone so that the viscosity of gained slurry is suitable for coating electrode, after super-dry, roll-in, make negative plate.
Adopting the conventional method preparation is that conductive agent, PAN are binding agent, LiNi with the carbon black
0.5Mn
0.5O
2Positive plate for active material.
In the dry negative plate of making, LiAl (SO
4)
2Additive accounts for 0.01 of negative material total weight, and conductive agent accounts for 0.07 of negative material total weight, and weight of binder accounts for 0.05 of negative material total weight, and negative electrode active material MCS accounts for 0.87 of negative material total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of negative active core-shell material is listed in the table 2.In the dry positive plate of making, positive electrode active materials LiNi
0.5Mn
0.5O
2Weight account for 0.85 of positive electrode total weight.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 21-24
According to the method among the embodiment 20, prepare a series of lithium secondary battery anodes that contain nanometer additive.Main difference between each embodiment is added nanometer additive kind difference.According to the heterogeneity of additive and conductive agent and positive electrode active materials, their content is separately adjusted to some extent.
Adopt conventional method to prepare conventional positive plate.
The consumption of employed conductive agent, binding agent and coordinative solvent and nanometer additive is listed in the table 1 among each embodiment, and the related data of electrode active material is listed in the table 2.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 25
According to second method, be the Al of 50 nanometers with average particle size
2O
3Nanometer additive, average particle size are that the conductive agent carbon black of 70 nanometers and active cathode material native graphite that average particle size is 3000 nanometers evenly mix, add the acetone soln of binding agent PAN and an amount of solvent acetone then so that the viscosity of gained slurry is suitable for coating electrode, make negative plate through after the dry roll-in.
Adopt the conventional method preparation with LiNi
0.5Mn
0.5O
2Positive plate for active material.
In the dry negative plate of making, Al
2O
3Additive accounts for 10 of negative material total weight
-6, the conductive agent carbon black accounts for 0.1 of negative material total weight, and binding agent accounts for 0.05 of negative material total weight, and the negative electrode active material native graphite accounts for 0.85 of negative material total weight.The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of negative active core-shell material is listed in the table 2.In the dry positive plate of making, positive electrode active materials LiNi
0.5Mn
0.5O
2Weight account for 0.85 of positive electrode total weight.
The consumption of employed conductive agent, binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 26-29
According to the method among the embodiment 25, prepare a series of lithium secondary battery anodes that contain nanometer additive.Main difference between each embodiment is added nanometer additive kind difference.According to the heterogeneity of additive and conductive agent and positive electrode active materials, their content is separately adjusted to some extent.
Adopt conventional method to prepare conventional positive plate.
The consumption of binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of negative active core-shell material is listed in the table 2.In the dry positive plate of making, the weight of positive electrode active materials accounts for 0.85 of positive electrode total weight.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
According to the third method, be the AlPO of 4000 nanometers with average particle size
4Additive, average particle size are after conductive agent carbon black, binding agent PAN and the average particle size of 120 nanometers is the negative active core-shell material SnSb alloy mixing of 500 nanometers, to add the solvent cyclopentanone, make the suitable slurry of viscosity.Coat electrode with conventional method, and drying, roller process, conventional negative plate obtained.Behind solvent cyclopentanone dispersing nanometer additive, the slurry of nanometer additive is coated on the above electrode slice, after super-dry, roll-in, make negative plate.
Adopt the conventional method preparation with LiMn
2O
4Conventional positive plate for active material.
In the dry negative plate of making, AlPO
4Additive accounts for 0.1 of negative material total weight, and the conductive agent carbon black accounts for 0.1 of negative material total weight, and binding agent PVdF accounts for 0.05 of negative material total weight, and negative electrode active material SnSb alloy accounts for 0.75 of negative material total weight.The kind of binding agent and coordinative solvent and nanometer additive and consumption are listed in the table 1, and the related data of negative active core-shell material is listed in the table 2.In the dry positive plate of making, the weight of positive electrode active materials accounts for 0.85 of positive electrode total weight.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the assembling of the method for embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 31-34
According to the method among the embodiment 30, prepare a series of lithium secondary battery anodes that contain nanometer additive.Main difference between each embodiment is added nanometer additive kind difference.According to the heterogeneity of additive and conductive agent and positive electrode active materials, their content is separately adjusted to some extent.The consumption of employed conductive agent, binding agent and coordinative solvent and nanometer additive is listed in the table 1 among each embodiment, and the related data of electrode active material is listed in the table 2.
Adopt conventional method to prepare conventional positive plate.
With this negative plate is negative pole, with conventional positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 35
With Li
2CO
3Be nanometer additive, prepare positive plate, prepare negative plate by the method for embodiment 20 by embodiment 05 method.The consumption of employed conductive agent, binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
With this negative plate is negative pole, with this positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
Embodiment 36
With AlPO
4Be nanometer additive, prepare positive plate, prepare negative plate by the method for embodiment 30 by the method for embodiment 10.The consumption of employed conductive agent, binding agent and coordinative solvent and nanometer additive is listed in the table 1, and the related data of electrode active material is listed in the table 2.
With this negative plate is negative pole, with this positive plate positive pole (negative electrode active material is excessive), according to the method assembled battery of embodiment 01 and carry out the constant current charge-discharge circulation and the calorifics measurement.The statistics loop-around data of positive active material is listed in table 2.
The kind and the consumption of the additive that uses among table 1, each embodiment
The kind and the consumption of the electrochemistry cycle performance of the kind consumption of the electrode active material that uses and specification and positive electrode active materials among table 2, each embodiment
Annotate:
1, the unit of capacity is MAH/gram, and the unit of additive granules degree is a nanometer;
2, above institute mark capacity is the specific capacity of positive electrode; When calculating specific capacity,, promptly only count the quality of positive electrode active materials part with the quality deduction of nanometer additive; In all are measured, adopt the excessive method of negative material to determine the specific capacity of positive electrode;
3, in embodiment 01-19, only in positive electrode, use additive; In embodiment 20-34, only in negative material, use additive; In embodiment 35-36, in anodal and negative material, use additive simultaneously.
Claims (7)
1, a kind of preparation method who contains the lithium secondary battery electrode of nanometer additive comprises following step:
1) nano material, binding agent and conventional electrodes active material are mixed;
The addition of described nano material accounts for 10 of electrode material total weight
-7～0.2 times;
Described binding agent is that Kynoar is or/and polyacrylonitrile;
Described binding agent accounts for 0.001～0.2 times of electrode material total weight;
Described conventional electrodes active material accounts for 0.2～0.99 times of electrode material total weight;
Described nano material is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 1～5000 nanometer;
Described nano material is one or more the mixture that is selected from following various types of materials:
When i) preparing positive plate, described nano material is selected from metal or nonmetallic simple substance material, comprises Li, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, lanthanide series metal, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi, Po, At, Ra, actinide metals;
When ii) preparing positive plate or negative plate, described nano material is selected from:
A) by above-mentioned i) described in metal or the nonmetal oxide that forms;
Perhaps by above-mentioned i) described in metal or the nonmetal composite oxides that form;
Described metal or nonmetal oxide are selected from MgO, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, Y
2O
3, La
2O
3, Fe
2O
3, MnO
2, ZrO
2, ZnO, CeO
2
Described metal or nonmetallic composite oxides are selected from LiCr
2O
4, LiAlO
2, LiCoO
2, LiNiO
2, LiMn
2O
4
B) described metal above-mentioned i) or nonmetallic salt;
Perhaps above-mentioned i) described metal in or nonmetallic double salt;
Described metal or nonmetallic salt are selected from Li
3PO
4, AlPO
4, Mg
3(PO
4)
2, Li
2CO
3, NaAlO
2, Li
2ZrO
3Or LiAlO
2
Described metal or nonmetallic double salt are selected from LiAl (SO
4)
2Or LiMPO
4, wherein, M is Mg, Al, Fe, Co, Ni, Zr, Cr, Ti or V;
2) add solvent in the mixture that step 1) obtains, 30～200 ℃ of stirrings, make binding agent dissolving wherein, mixture forms uniform sizing material, coats electrode according to conventional method, after drying, the roller process, uses as electrode;
Described solvent is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more;
The weight of described solvent accounts for 0.2～1000 times of electrode material total weight.
2, the preparation method who contains the lithium secondary battery electrode of nanometer additive as claimed in claim 1 is characterized in that, also is included in the mixture of step 1) to add conductive additive;
Described conductive additive is the mixture that is selected from carbon black, acetylene black, metal powder and the metallic fiber one or more;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 5 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
3, a kind of preparation method who contains the lithium secondary battery electrode of nanometer additive comprises following step:
1) nano material and conventional electrodes active material are mixed;
The addition of described nano material accounts for 10 of electrode material total weight
-7～0.2 times;
Described conventional electrodes active material accounts for 0.2～0.99 times of electrode material total weight;
Described nano material is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 1～5000 nanometer;
Described nano material is one or more the mixture that is selected from following various types of materials:
When i) preparing positive plate, described nano material is selected from metal or nonmetallic simple substance material, comprises Li, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, lanthanide series metal, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi, Po, At, Ra, actinide metals;
When ii) preparing positive plate or negative plate, described nano material is selected from:
A) by above-mentioned i) described in metal or nonmetal formed oxide;
Perhaps by above-mentioned i) described in metal or nonmetal formed composite oxides;
Described metal or nonmetal oxide are selected from MgO, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, Y
2O
3, La
2O
3, Fe
2O
3, MnO
2, ZrO
2, ZnO, CeO
2
Described metal or nonmetallic composite oxides are selected from LiCr
2O
4, LiAlO
2, LiCoO
2, LiNiO
2, LiMn
2O
4
B) described metal above-mentioned i) or nonmetallic salt;
Perhaps above-mentioned i) described metal in or nonmetallic double salt;
Described metal or nonmetallic salt are selected from Li
3PO
4, AlPO
4, Mg
3(PO
4)
2, Li
2CO
3, NaAlO
2, Li
2ZrO
3Or LiAlO
2
Described metal or nonmetallic double salt are selected from LiAl (SO
4)
2Or LiMPO
4, wherein, M is Mg, Al, Fe, Co, Ni, Zr, Cr, Ti or V;
2) at 30～200 ℃, binding agent and solvent are mixed with the solution of binding agent, the weight of binding agent accounts for 0.001～0.2 times of total solution weight in the solution;
Described binding agent is that Kynoar is or/and polyacrylonitrile;
Described solvent is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more;
The weight of described solvent accounts for 0.2～1000 times of electrode material total weight;
3) with step 2) in the binder solution that obtains join in the mixture of step 1), mix once more, the slurry of making coats electrode according to conventional method, after drying, the roller process, uses as electrode;
Described binding agent accounts for 0.001～0.2 times of electrode material total weight.
4, the preparation method who contains the lithium secondary battery electrode of nanometer additive as claimed in claim 3 is characterized in that, also is included in the mixture of step 1) to add conductive additive;
Described conductive additive is the mixture that is selected from carbon black, acetylene black, metal powder and the metallic fiber one or more;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 10 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
5, the preparation method who contains the lithium secondary battery electrode of nanometer additive as claimed in claim 3 is characterized in that, also is included in to add diluent in the step 3); Described diluent is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more; Addition is 0.1～1000 times of binder solution volume.
6, a kind of preparation method who contains the lithium secondary battery electrode of nanometer additive comprises following step:
1) electrode active material, binder solution and mixing diluents is even, coat electrode according to conventional method, make the conventional electrodes sheet through super-dry, roll-in then;
The weight of the binding agent in the described binder solution accounts for 0.001～0.2 times of total solution weight; Described binding agent is that Kynoar is or/and polyacrylonitrile; Described solvent is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more;
Described diluent is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more; Described diluent accounts for 0.2～100 times of electrode material total weight;
Described electrode active material accounts for 0.2～0.99 times of electrode material total weight;
2) nano material is evenly mixed with dispersant, make suspension-turbid liquid, evenly coat on the electrode slice that step 1) makes, through obtaining the negative or positive electrode sheet after dry, the roll-in once more;
Described dispersant is the mixture that is selected from N-methyl pyrrolidone, acetone and the cyclopentanone one or more;
The content of nano material accounts for 10 of suspension-turbid liquid total weight in the described suspension-turbid liquid
-6～0.2 times;
The addition of described nano material accounts for 10 of electrode material total weight
-7～0.2 times;
Described nano material is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 1～5000 nanometer;
Described nano material is one or more the mixture that is selected from following various types of materials:
When i) preparing positive plate, described nano material is selected from metal or nonmetallic simple substance material, comprises Li, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, Se, Rb, Sr, Y, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Cd, In, Sn, Sb, Te, Ba, lanthanide series metal, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Bi, Po, At, Ra, actinide metals;
When ii) preparing positive plate or negative plate, described nano material is selected from:
A) by above-mentioned i) described in metal or nonmetal formed oxide;
Perhaps by above-mentioned i) described in metal or nonmetal formed composite oxides;
Described metal or nonmetal oxide are selected from MgO, Al
2O
3, SiO
2, SnO, TiO
2, SnO
2, V
2O
5, Y
2O
3, La
2O
3, Fe
2O
3, MnO
2, ZrO
2, ZnO, CeO
2
Described metal or nonmetallic composite oxides are selected from LiCr
2O
4, LiAlO
2, LiCoO
2, LiNiO
2, LiMn
2O
4
B) the described metal above-mentioned i) or nonmetallic salt or double salt;
Described metal or nonmetallic salt are selected from Li
3PO
4, AlPO
4, Mg
3(PO
4)
2, Li
2CO
3, NaAlO
2, Li
2ZrO
3Or LiAlO
2
Described metal or nonmetallic double salt are selected from LiAl (SO
4)
2Or LiMPO
4, wherein, M is Mg, Al, Fe, Co, Ni, Zr, Cr, Ti or V.
7, the preparation method who contains the lithium secondary battery electrode of nanometer additive as claimed in claim 6 is characterized in that, also is included in the mixture of step 1) to add conductive additive;
Described conductive additive is the mixture that is selected from carbon black, acetylene black, metal powder and the metallic fiber one or more;
Described conductive additive is graininess, fibrous, laminar, bar-shaped or banded material, and at least in one direction its size between 10 nanometers～10 micron;
Described conductive additive accounts for 0.001～0.2 times of electrode material total weight.
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|---|---|---|---|
| CNB2005100865125A CN100446307C (en) | 2005-09-23 | 2005-09-23 | Method for preparing lithium secondary cell electrode containing nano additive |
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| CN100446307C true CN100446307C (en) | 2008-12-24 |
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| CN102208648A (en) * | 2010-03-31 | 2011-10-05 | 比亚迪股份有限公司 | Secondary battery electrode and secondary battery |
| CN102420323B (en) * | 2011-03-03 | 2014-03-19 | 中国科学院宁波材料技术与工程研究所 | Electrode composite material of lithium secondary battery and preparation method thereof |
| CN102593440A (en) * | 2011-12-01 | 2012-07-18 | 湖北中能锂电科技有限公司 | Cathode materials for lithium ion battery and producing method thereof |
| CN102891316B (en) * | 2012-10-11 | 2015-04-01 | 中国科学院过程工程研究所 | Lithium iron vanadium manganese phosphate nano oxide compound anode material and preparation method thereof |
| CN102903930B (en) * | 2012-10-23 | 2016-06-08 | 中国科学院过程工程研究所 | A kind of lithium rechargeable battery and preparation method thereof |
| CN103117382B (en) * | 2013-02-25 | 2015-07-08 | 江苏乐能电池股份有限公司 | Preparation method of lithium ion battery negative pole material capable of improving safety performance |
| CN103151505B (en) * | 2013-03-01 | 2016-01-13 | 中国科学院过程工程研究所 | A kind of Lithium-titanate composite negative pole and preparation method thereof |
| CN103413930B (en) * | 2013-07-30 | 2015-09-09 | 南京航空航天大学 | The LiNi1/2Mn3/2O4 positive electrode of lithium ion conductor Li2MO3 (M=Ti, Si, Zr) coating modification and preparation method |
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| CN105355849B (en) * | 2015-11-18 | 2017-11-03 | 中航锂电（洛阳）有限公司 | Cathode of lithium battery additive, lithium ion battery, preparation method and application |
| CN105489897B (en) * | 2015-11-27 | 2018-05-04 | 中航锂电（洛阳）有限公司 | Ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery |
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| CN108878890B (en) * | 2017-05-12 | 2021-09-03 | 中南大学 | Lithium ion battery conductive film/metallic lithium/conductive substrate three-layer structure composite electrode and preparation method thereof |
| CN108376764B (en) * | 2018-03-23 | 2020-07-28 | 西北工业大学 | Surface modification method for negative electrode of lithium secondary battery, Ag modified lithium electrode prepared by using method and application |
| CN108987705B (en) * | 2018-07-17 | 2020-12-18 | 深圳市优特利电源有限公司 | Electrode material composition, lithium ion battery positive plate and lithium ion battery |
| CN110137436B (en) * | 2019-03-14 | 2022-04-26 | 青海师范大学 | Method for improving lithium iron phosphate discharge platform |
| CN112151742A (en) * | 2020-09-25 | 2020-12-29 | 福建师范大学 | Preparation method of ternary cathode material modified by metal oxide and graphene and used for improving performance of full battery |
| CN112151807A (en) * | 2020-09-27 | 2020-12-29 | 湖南杉杉能源科技股份有限公司 | Lithium ion battery positive pole piece and preparation method thereof |
| CN114824444A (en) * | 2022-05-20 | 2022-07-29 | 湖南时代联合新能源有限公司 | Water-based lithium manganate battery and preparation method thereof |
| CN117457856B (en) * | 2023-12-20 | 2024-03-12 | 清陶(昆山)能源发展股份有限公司 | Composite positive electrode and preparation method thereof |
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