CN105489897B - Ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery - Google Patents

Ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery Download PDF

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CN105489897B
CN105489897B CN201510849084.0A CN201510849084A CN105489897B CN 105489897 B CN105489897 B CN 105489897B CN 201510849084 A CN201510849084 A CN 201510849084A CN 105489897 B CN105489897 B CN 105489897B
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parts
lithium ion
ion battery
liquid
lithium
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CN105489897A (en
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徐小龙
辛晓冬
粱梦伟
陈天振
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China Lithium Battery Technology Co Ltd
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China Aviation Lithium Battery Co Ltd
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B82NANOTECHNOLOGY
    • B82YSPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00Nanotechnology for materials or surface science, e.g. nanocomposites
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

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  • Crystallography & Structural Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention relates to a kind of ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery, belong to technical field of lithium ion.The ternary cathode material of lithium ion battery of the present invention includes the component of following parts by weight with conduction liquid:13 parts of carbon nanotubes, 13 parts of carbon black, 0.1 1 parts of lithium salts, 0.1 1 parts of ionic liquid, 5 20 parts of binding agent, 100 parts of solvent, the lithium salts are lithium metaaluminate.The ternary cathode material of lithium ion battery conduction liquid of the present invention can improve the imbibition liquid-keeping property of anode pole piece used in ternary lithium ion battery, reduce the internal resistance of battery, and improve the cycle performance and security performance of battery charge and discharge cycles under larger multiplying power.

Description

Ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion Battery
Technical field
The present invention relates to a kind of ternary cathode material of lithium ion battery conduction liquid and preparation method thereof, lithium ion battery, Belong to technical field of lithium ion.
Background technology
With the fast development of New Energy Industry, the application range of lithium ion battery is more and more extensive, is not only set in electronics The traditional field such as standby occupies most of market, and is also at leading position in new-energy automobile field, this mainly have benefited from from Sub- battery energy density is high, cycle life is good, advantages of environment protection.Existing lithium ion battery by the positive electrode used not With that can be divided into cobalt acid lithium battery, ferric phosphate lithium cell, lithium manganate battery, ternary material battery etc., wherein cobalt acid lithium is due to environment With cost problem in new-energy automobile field using less, and the energy density of ferric phosphate lithium cell is relatively low, lithium manganate battery Cycle life it is poor, limit further development of both batteries in new-energy automobile field, the energy of ternary battery is close Degree is higher, is considered as the ideal power lithium-ion battery of electric automobile.However, the security of ternary material battery is poor, Security performance when being particularly fabricated to high capacity cell is difficult up to standard.
To improve the security of ternary material battery, current method mainly has:Electrolyte safe to use, safety in utilization Can high ceramic diaphragm or its select high tertiary cathode material of security performance etc., still, these methods are to ternary material electricity The security raising in pond is very limited, can not fundamentally solve the safety issue of ternary battery.
Application publication number is that the Chinese invention patent of CN104766959A discloses a kind of preparation method of ternary material, is led to Cross and coat lithium metaaluminate on the surface of ternary material, the ternary material of cladding is made, reduces the internal resistance of material, improves battery Cycle performance and security.But imbibition liquid-keeping property of the program for ternary material influence it is little, battery carry out compared with During high rate charge-discharge, the raising of its cycle performance and unobvious.Further, since the program is needed in ternary material particle surface Coated, its coating thickness is difficult to control, and coating thickness is huge to the Electrochemical Performances of material, therefore, should Scheme is for large-scale industrialization production and does not apply to.Moreover, program cladding process is also higher to process control needs, and High temperature sintering again is needed, adds production cost, weakens advantage of the ternary material relative to other materials.
Appropriate additive is added during positive electrode closes slurry to improve the performance of battery, to the production technology of battery Influence less, will not excessively increase production cost.Conductive agent is that positive electrode closes a kind of additive often added during slurry, such as Application publication number is that the Chinese invention patent of CN101710619A discloses electrode plates and its making of a kind of lithium ion battery Method, specifically discloses and combined conductive agent is added in positive active material, and combined conductive agent is multi-layer graphene, carbon nanotubes And carbon black etc., the program can improve the electric conductivity of positive electrode and the fast charging and discharging ability of battery, but to ternary material For, its security and cycle performance are had little to no effect.Therefore, exploitation one kind can improve tertiary cathode material imbibition and Liquid-keeping property, improves cycle performance of the battery under larger multiplying power and seems significant.
The content of the invention
It is an object of the invention to provide a kind of ternary cathode material of lithium ion battery conduction liquid, to improve tertiary cathode Material imbibition and liquid-keeping property simultaneously improve cycle performance of the battery under larger multiplying power.The present invention also aims to provide one kind The preparation method of the conduction liquid and the lithium ion battery using the conduction liquid.
In order to realize the above object the technical solution of the ternary cathode material of lithium ion battery conduction liquid of the present invention is such as Under:
A kind of ternary cathode material of lithium ion battery conduction liquid, includes the component of following parts by weight:Carbon nanotubes 1-3 Part, 1-3 parts of carbon black, 0.1-1 parts of lithium salts, 0.1-1 parts of ionic liquid, 5-20 parts of binding agent, 100 parts of solvent, the lithium salts is inclined Lithium aluminate.
The conduction liquid of the present invention is by addition with steam forces down, heat endurance is good, not volatile, solvability is strong, ring The carbon nanotubes that border is friendly, the ionic liquid of electrochemical stability window and conductivity height, imbibition ability are strong, and combine inclined companion's acid lithium The cooperative effect between these three materials is played, improves the imbibition liquid-keeping property of tertiary cathode material, and reduces battery Internal resistance, improves security performance, the cycle performance of ternary lithium ion battery.
The ionic liquid is -2 methylpyrazole sodium tetrafluoroborate of 1- ethyls, two (trifluoromethyl of N- Methyl-N-propyls piperidines Sulphonyl) one kind in imines (PP13TFSI).
The binding agent is any one in PVDF, Sodium Polyacrylate, polyacrylonitrile.
The solvent is any one in 1-methyl-2-pyrrolidinone (NMP), dimethylformamide.
The technical solution of the ternary cathode material of lithium ion battery conduction liquid of the present invention is as follows:
The preparation method of above-mentioned ternary cathode material of lithium ion battery conduction liquid, includes the following steps:
1) 2.5-10 parts by weight binder is added in 50 parts by weight solvent and binder solution is made, by 1-3 parts by weight carbon Nanotube, 1-3 parts by weight of carbon black per are added in the binder solution, add 0.1-1 parts by weight lithium salts, dispersed, are obtained scattered Liquid A;
Under conditions of dew point is not higher than -50 DEG C, 0.1-1 parts by weight ionic liquid, 2.5-10 parts by weight binder are added Enter in 50 parts by weight solvent, it is dispersed, obtain dispersion liquid B;
2) under conditions of dew point is not higher than -50 DEG C, dispersion liquid B is added in dispersion liquid A, is uniformly dispersed, to obtain the final product.
The preparation method of the ternary cathode material of lithium ion battery conduction liquid of the present invention is easy to operate, and production cost is low, Suitable for large-scale industrialized production.
Dispersed in the step 2) is mechanical agitation 5-6h.
In order to improve be uniformly dispersed degree of the ionic liquid in system, it is incorporated as being added dropwise in step 2).
In order to improve dispersion efficiency, the adition process of step 2) is carried out at the same time stirring.
In order to improve the degree of being uniformly dispersed, dispersed in step 1) uses ultrasonic disperse.
Liquid is protected in the imbibition that the ternary cathode material of lithium ion battery conduction liquid of the present invention can improve tertiary cathode material Ability, reduces the internal resistance of battery, and improves the cycle performance and security performance of battery charge and discharge cycles under larger multiplying power.This hair The carbon nanotubes added in bright conduction liquid has higher specific surface area, can improve the imbibition liquid-keeping property of material;This hair Bright conduction liquid is added with highly conductive carbon nanotubes, and the effect of assisting ion liquid, the direct current of obtained lithium ion battery Internal resistance reduces significantly, simultaneously because ionic liquid can improve battery structure stability, carbon nanotubes and ion again Liquid, which acts synergistically, can improve the cycle performance of lithium ion battery, and the security performance of lithium ion battery is also far superior to existing skill The security performance of lithium ion battery in art.
Brief description of the drawings
Fig. 1 is the circulation using lithium ion battery made from the ternary cathode material of lithium ion battery conduction liquid of the present invention Curve.
Embodiment
Technical scheme is further detailed with reference to specific embodiment.
Embodiment 1
The ternary cathode material of lithium ion battery conduction liquid of the present embodiment, is made of the component of following parts by weight:Carbon Nanotube 2g, carbon black 2g, lithium metaaluminate 0.5g, (trimethyl fluoride sulfonyl) imines of ionic liquid trimethyl two 0.5g, bonding Agent PVDF 10g, solvent NMP 100g.
The preparation method of above-mentioned ternary cathode material of lithium ion battery conduction liquid includes the following steps:
1) 5g binding agents PVDF is added in 50g solvents NMP, is uniformly mixed and binder solution is made, then receive 2g carbon Mitron, 2g carbon blacks are added in the binder solution, add 0.5g lithium metaaluminates after mixing, and ultrasonic disperse is uniform, are made and are divided Dispersion liquid A;
2) in the environment of dew point≤- 50 DEG C, 5g binding agents PVDF is added in 50g solvents NMP, be uniformly mixed be made it is viscous Agent solution is tied, -2 methylpyrazole sodium tetrafluoroborate of 0.5g ionic liquid 1- ethyls is added in the binder solution, ultrasound is stirred Mix uniform dispersion liquid B;
3) in the environment of dew point≤- 50 DEG C, under mechanical agitation, dispersion liquid B is slowly dropped to dispersion liquid A In, then mechanical agitation 6h again, obtains stable oiliness conduction liquid, to obtain the final product.
The lithium ion battery of the present embodiment, first by above-mentioned ternary cathode material of lithium ion battery conduction liquid and ternary material Li(Ni0.5Co0.3Mn0.2)O2Mixing, is made anode sizing agent, and coated, roller cutting is for positive plate;Using graphite as negative material Negative plate is made;In the electrolyte used, LiPF6Concentration is 1.3mol/L, and solvent forms for the EC and DEC of volume ratio 1: 1 Mixed solvent;Using 2400 films of Celgard as membrane;The lithium ion battery of 5Ah is made according to method of the prior art.
Embodiment 2
The ternary cathode material of lithium ion battery conduction liquid of the present embodiment, is made of the component of following parts by weight:Carbon Nanotube 1g, carbon black 1g, lithium metaaluminate 0.1g, ionic liquid N-Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines (PP13TFSI) 0.1g, binding agent polyacrylic acid 5g, solvent dimethylformamide 100g.
The preparation method of above-mentioned ternary cathode material of lithium ion battery conduction liquid includes the following steps:
1) 2.5g binding agents polyacrylic acid is added in 50g solvent dimethylformamides, is uniformly mixed and binder solution is made, Then 1g carbon nanotubes, 1g carbon blacks are added in the binder solution, adds 0.1g lithium metaaluminates, ultrasonic disperse after mixing Uniformly, dispersion liquid A is made;
2) in the environment of dew point≤- 50 DEG C, 2.5g binding agents polyacrylic acid is added in 50g solvent dimethylformamides, It is uniformly mixed and binder solution is made, 0.1g ionic liquid Ns-Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines is added Enter into the binder solution, ultrasonic agitation is uniform to obtain dispersion liquid B;
3) in the environment of dew point≤- 50 DEG C, under mechanical agitation, dispersion liquid B is slowly dropped to dispersion liquid A In, then mechanical agitation 5h again, obtains stable oiliness conduction liquid, to obtain the final product.
The lithium ion battery of this present embodiment, first by above-mentioned ternary cathode material of lithium ion battery conduction liquid and ternary material Expect Li (Ni0.5Co0.3Mn0.2)O2Mixing, is made anode sizing agent, and coated, roller is cut, and prepares positive plate;Using graphite as anode material Negative plate is made in material;In the electrolyte used, LiPF6Concentration is 1.3mol/L, and solvent forms for the EC and DEC of volume ratio 1: 1 Mixed solvent;Using 2400 films of Celgard as membrane;The lithium ion battery of 5Ah is made according to method of the prior art.
Embodiment 3
The ternary cathode material of lithium ion battery conduction liquid of the present embodiment, is made of the component of following parts by weight:Carbon Nanotube 3g, carbon black 3g, lithium metaaluminate 1.0g, ionic liquid N-Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines (PP13TFSI) 1.0g, binding agent polyacrylonitrile 20g, solvent NMP 100g.
The preparation method of above-mentioned ternary cathode material of lithium ion battery conduction liquid includes the following steps:
1) 5g binding agents polyacrylonitrile is added in 50g solvents NMP, is uniformly mixed and binder solution is made, then by 3g Carbon nanotubes, 3g carbon blacks are added in the binder solution, add 1.0g lithium metaaluminates after mixing, and ultrasonic disperse is uniform, system Obtain dispersion liquid A;
2) in the environment of dew point≤- 50 DEG C, 5g binding agents polyacrylonitrile is added in 50g solvents NMP, is uniformly mixed system Into binder solution, 1.0g ionic liquid Ns-Methyl-N-propyl piperidines two (trimethyl fluoride sulfonyl) imines is added to the bonding In agent solution, ultrasonic agitation is uniform to obtain dispersion liquid B;
3) in the environment of dew point≤- 50 DEG C, under mechanical agitation, dispersion liquid B is slowly dropped to dispersion liquid A In, then mechanical agitation 6h again, obtains stable oiliness conduction liquid, to obtain the final product.
The lithium ion battery of the present embodiment, with above-mentioned ternary cathode material of lithium ion battery conduction liquid and ternary material Li (Ni0.5Co0.3Mn0.2)O2Mixing, is made anode sizing agent, and is cut by coating, roller, prepares positive plate;Using graphite as negative material Negative plate is made;In the electrolyte used, LiPF6Concentration is 1.3mol/L, and solvent forms for the EC and DEC of volume ratio 1: 1 Mixed solvent;Using 2400 films of Celgard as membrane;The lithium ion battery of 5Ah is made according to method of the prior art.
Comparative example
Using the SP conductive agents that market is purchased as positive conductive agent and with ternary material Li (Ni0.5Co0.3Mn0.2)O2Mixing As positive electrode, slurry is closed, prepares positive plate;Negative plate is made by negative material of graphite;In the electrolyte used, LiPF6 Concentration is 1.3mol/L, and solvent is the mixed solvent that the EC and DEC of volume ratio 1: 1 are formed;Using 2400 films of Celgard as membrane; The lithium ion battery of 5Ah is made according to method of the prior art.
Experimental example
1) the imbibition liquid-keeping property test of positive plate.
The imbibition liquid-keeping property of obtained positive plate, test result are as shown in table 1 in testing example 1-3 and comparative example.
The imbibition liquid-keeping property of obtained positive plate in 1 embodiment 1-3 of table and comparative example
Rate of liquid aspiration (mL/min) Protect liquid rate (24h electrolyte contents/0h electrolyte contents)
Embodiment 1 7.2 95.3%
Embodiment 2 6.5 94.2%
Embodiment 3 6.4 94.4%
Comparative example 3.1 83.7%
2) electrochemical property test of lithium ion battery.
The DC internal resistance of obtained lithium ion battery, discharge capacitance (electric discharge in testing example 1-3 and comparative example Capacity retention ratio=termination capacity/initial capacity), and according to following condition test its circulation 200 times, 300 times, 400 times, 500 Secondary capacity retention ratio:1.0C multiplying powers charge, and 1.0C multiplying power dischargings, test voltage scope is 2.7-4.2V.Test result such as table 2 Shown in Fig. 1.
The chemical property of obtained lithium ion battery in 2 embodiment 1-3 of table and comparative example
3) security test.
Obtained lithium ion battery in embodiment 1-3 and comparative example is respectively taken 10, carries out acupuncture short circuit experiment respectively, is surveyed The safety loading coefficient of lithium ion battery is tried, its safety loading coefficient is total for (number of batteries of battery sum-short-circuit fire)/battery Number, test result are as shown in table 3.
The security of obtained lithium ion battery in 3 embodiment 1-3 of table and comparative example
Safety loading coefficient
Embodiment 1 9/10
Embodiment 2 8/10
Embodiment 3 9/10
Comparative example 4/10
As can be seen from Table 1, the ternary cathode material of lithium ion battery conduction liquid of the present invention is added, the imbibition of pole piece is protected Liquid energy power is strengthened, the reason for this is that carbon nanotubes has higher specific surface area, can improve the imbibition liquid-keeping property of material.
As can be seen from Table 2, lithium ion made from the ternary cathode material of lithium ion battery conduction liquid of the present invention is added The DC internal resistance of battery reduces significantly, and reason is probably that the conduction liquid of the present invention is added with highly conductive carbon nanometer Pipe, and the effect of assisting ion liquid.
As can be seen from Table 2, the cycle performance of lithium ion battery of the invention is improved largely, bright in each stage It is aobvious to be better than comparative example.The reason for this is that bigger serface possessed by carbon nanotubes strengthens the imbibition liquid-keeping property of positive electrode, Simultaneously because ionic liquid can improve battery structure stability again, so as to improve the cycle performance of lithium ion battery.
As can be seen from Table 3,10 batteries of embodiment 1 and embodiment 3 respectively have 1 short circuit to catch fire in acupuncture experiment, 10 batteries of embodiment 2 have 2 short circuits to catch fire in acupuncture experiment, and 10 batteries of comparative example have in acupuncture experiment 6 short circuits are caught fire, therefore the security performance of the lithium ion battery of the present invention is far superior to the peace of lithium ion battery in the prior art Full performance.

Claims (8)

  1. A kind of 1. lithium ion battery anode glue size, it is characterised in that including tertiary cathode material and conduction liquid, the conduction liquid bag Include the component of following parts by weight:1-3 parts of carbon nanotubes, 1-3 parts of carbon black, 0.1-1 parts of lithium salts, 0.1-1 parts of ionic liquid, 5-20 parts of binding agent, 100 parts of solvent, the lithium salts are lithium metaaluminate;The ionic liquid is -2 methylpyrazole four of 1- ethyls Sodium fluoborate, N- Methyl-N-propyls piperidines two(Trimethyl fluoride sulfonyl)Any one in imines.
  2. 2. the lithium ion battery anode glue size as described in claim 1, it is characterised in that the binding agent is PVDF, polypropylene Acid, any one in polyacrylonitrile.
  3. 3. the lithium ion battery anode glue size as described in claim 1, it is characterised in that the solvent is N- crassitudes Any one in ketone, dimethylformamide.
  4. 4. the lithium ion battery anode glue size as described in claim 1, it is characterised in that the preparation of the conduction liquid is included such as Lower step:
    1)2.5-10 parts by weight binder is added in 50 parts by weight solvent binder solution is made, 1-3 parts by weight carbon is received Mitron, 1-3 parts by weight of carbon black per are added in the binder solution, add 0.1-1 parts by weight lithium salts, dispersed, are obtained scattered Liquid A;
    Under conditions of dew point is not higher than -50 DEG C, 0.1-1 parts by weight ionic liquid, 2.5-10 parts by weight binder are added It is dispersed in 50 parts by weight solvent, obtain dispersion liquid B;
    2)Under conditions of dew point is not higher than -50 DEG C, dispersion liquid B is added in dispersion liquid A, is uniformly dispersed, to obtain the final product.
  5. 5. lithium ion battery anode glue size as claimed in claim 4, it is characterised in that step 2)Described in be incorporated as being added dropwise.
  6. 6. lithium ion battery anode glue size as claimed in claim 5, it is characterised in that step 2)Described in add while into Row stirring.
  7. 7. lithium ion battery anode glue size as claimed in claim 4, it is characterised in that step 1)In dispersed use Ultrasonic disperse.
  8. A kind of 8. lithium ion battery, it is characterised in that its anode sizing agent using as described in claim 1-7 any one lithium from Sub- battery anode slurry.
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CN107069039A (en) * 2017-03-24 2017-08-18 江苏乐能电池股份有限公司 Oiliness conduction liquid and preparation method thereof used in a kind of ferric phosphate lithium cell
CN108735972B (en) * 2017-04-21 2022-11-15 昭和电工材料株式会社 Method for manufacturing battery member for secondary battery
CN108448076A (en) * 2018-02-09 2018-08-24 山东丰元化学股份有限公司 The method of modifying of nickle cobalt lithium manganate trielement composite material
CN110265719A (en) * 2019-06-04 2019-09-20 江西力能新能源科技有限公司 A kind of electrolyte and its preparation process of lithium battery

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CN1937285A (en) * 2005-09-23 2007-03-28 中国科学院物理研究所 Method for preparing lithium secondary cell electrode containing nano additive
CN104466098A (en) * 2014-12-25 2015-03-25 芜湖华欣诺电化学科技有限公司 Ionic-liquid-coated lithium ion battery positive plate as well as preparation method thereof and lithium ion battery
CN104752729A (en) * 2015-03-09 2015-07-01 李国富 Preparation method of aqueous composite binder having electronic and ionic conductivity generality for lithium ion battery

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CN104466098A (en) * 2014-12-25 2015-03-25 芜湖华欣诺电化学科技有限公司 Ionic-liquid-coated lithium ion battery positive plate as well as preparation method thereof and lithium ion battery
CN104752729A (en) * 2015-03-09 2015-07-01 李国富 Preparation method of aqueous composite binder having electronic and ionic conductivity generality for lithium ion battery

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