CN104766946A - Lithium ion battery positive pole piece, preparation method of positive pole piece and lithium ion battery - Google Patents
Lithium ion battery positive pole piece, preparation method of positive pole piece and lithium ion battery Download PDFInfo
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- CN104766946A CN104766946A CN201510171935.0A CN201510171935A CN104766946A CN 104766946 A CN104766946 A CN 104766946A CN 201510171935 A CN201510171935 A CN 201510171935A CN 104766946 A CN104766946 A CN 104766946A
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- ion battery
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- pole piece
- anode
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a lithium ion battery positive pole piece which comprises a current collector and a positive pole film, wherein the positive pole film consists of a positive pole active material, a conductive agent and an adhesive; and an organic high polymer substance layer is sprayed on the surface layer of the film and mainly consists of at least one of polyimide, polyvinylidene fluoride, polytetrafluoroethylene and polyacrylonitrile. The method for preparing the positive pole piece comprises the following steps: mixing the positive pole active material, the conductive agent and the adhesive, and adding the mixture into an organic solvent, thereby obtaining positive pole slurry; coating the positive pole slurry on the current collector, drying, thereby obtaining the positive pole piece; placing the positive pole piece on a heating plate in a fuming cupboard, spraying a soluble organic high polymer substance solution on the surface layer of the positive pole piece to form a soluble organic high polymer substance layer, drying, thereby obtaining the lithium ion battery positive pole piece. The positive pole piece can be assembled with a negative pole, a diaphragm and electrolyte to form the lithium ion battery disclosed by the invention. A high-voltage lithium ion battery environment can be met, and the cycle performance and rate capability of the lithium ion battery can be improved.
Description
Technical field
The invention belongs to technical field of lithium ion, the lithium ion battery particularly relating to a kind of based lithium-ion battery positive plate and preparation method thereof and make with it.
Background technology
Since rechargeable lithium ion batteries is realized commercialization first time in 1991 by SONY, different lithium transition metal oxide is (as LiCoO
2, LiNiO
2, LiMn
2o
4, LiFePO
4, LiFe (Mn) PO
4, LiNi
xco
ymn
(1-x-y)o
2(y≤1, x+y≤1) etc.) be successfully applied to field of lithium ion battery as positive electrode.
LiCoO
2be in lithium ion battery, realize business-like positive electrode, because it has high-energy-density and superior battery performance, and be easy to the advantages such as production, be considered to one of positive electrode of most attraction.LiCoO
2theoretical capacity be 272mAh/g, but when battery charge cutoff voltage is 4.2V, only have half lithium ion from LiCoO
2in deviate from, result causes specific discharge capacity in practical application to be only about 140mAh/g.Therefore, need to make more lithium ions from LiCoO
2in deviate from, to improve battery specific capacity and energy density.Research also finds, the moisture in lithium-ion battery electrolytes can cause LiPF
6decompose, form HF, HF and can accelerate LiCoO
2dissolving, when charging voltage is more than 4.2V, part LiCoO
2be dissolved in electrolyte, cause capacity in circulating battery process significantly to be decayed.In this case, should pay close attention to and slow down LiCoO
2capacity attenuation to meet the application at lithium ion battery.
Charge and discharge cycles and the positive electrode surface chemistry of lithium ion battery are closely related, effectively can be reduced the dissolving of positive electrode by coated effects on surface modification.Many metal oxides are (as TiO
2, Al
2o
3, ZrO
2with MgO etc.) successfully achieve Surface coating, the people such as Jang-Hoon Park report and utilize organic substance PI clad anode material, application number has been the Introduction To Cn Patent of 201310014237.0 to the inorganic, metal oxide of positive electrode and charcoal/nitrogen type organic double-coated, ground floor is metal oxide, and the second layer is organic substance.These methods can effectively intercept positive electrode and directly contact with electrolyte, keep ionic conduction path unobstructed simultaneously, suppress the release of phase transformation and oxygen, can also reduce the lack of alignment of cation in crystal.But easily come off after metallic oxide cladded anode material, there is coated uneven problem; Coated with Organic Matter positive electrode is closely bonding, can adapt to high-voltage lithium ion batteries, but coating layer affects the conduction velocity of ion and electronics, causes battery performance not good.
In addition, application number be 201210000156.0 Chinese patent literature in the coating of positive electrode active materials upper epidermis, there is the Polymer Tie-layer of cementation, though this method can strengthen mechanical performance and the security performance of battery, but the polymeric layer after coating only plays cementation, and thickness is bigger than normal, in battery charge and discharge process, deviating from and embedding quantity of lithium ion can be hindered, thus can battery performance be affected.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided a kind of anode slice of lithium ion battery that can adapt to high-voltage lithium ion batteries environment, circulating battery and high rate performance can also be improved to a certain extent, also the corresponding lithium ion battery a kind of preparation method of this simple anode slice of lithium ion battery being provided and being obtained by it.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of anode slice of lithium ion battery, comprise collector and coating positive pole diaphragm on a current collector, described positive pole diaphragm forms primarily of positive electrode active materials, conductive agent and binding agent, the top layer spraying polymer layer of described positive pole diaphragm, the thickness h≤100nm of described polymer layer; The main constituent of described polymer layer is at least one in polyimides (PI), Kynoar (PVDF), polytetrafluoroethylene (PTFE), polyacrylonitrile (PAN).
Technique scheme of the present invention, by spraying polymer layer, makes polymer have excellent ion, electron conduction, and can clad anode diaphragm thus suppress the loss of active material in charge and discharge process.
In above-mentioned anode slice of lithium ion battery, preferred: the thickness h≤50nm of described polymer layer, described polymer layer is discontinuous spot distribution.
In above-mentioned anode slice of lithium ion battery, preferred: described positive electrode active materials is LiCoO
2, LiNi
xco
ymn
(1-x-y)o
2, LiMn
2o
4, LiFePO
4in at least one, wherein y≤1, x+y≤1, the proportioning of described positive electrode active materials, conductive agent and binding agent is 94 ~ 96: 3 ~ 2: 3 ~ 2.
In above-mentioned anode slice of lithium ion battery, preferred: described positive electrode active materials is LiCoO
2, and LiCoO
2d50>=5 μm (preferred D50>=13 μm, particularly preferably D50>=18 μm); The proportioning of described positive electrode active materials, conductive agent and binding agent is 94: 3: 3; The main constituent of described polymer layer is polyimides.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned anode slice of lithium ion battery, comprises the following steps:
(1) described positive electrode active materials, conductive agent, binding agent are mixed in mass ratio, add after in organic solvent and repeatedly stir until evenly, obtain anode sizing agent; Anode sizing agent is coated on collector (such as aluminium foil) subsequently, dries under being placed on vacuum drying chamber, obtain anode pole piece;
(2) anode pole piece is placed on the heating plate of fume hood, the temperature of heating plate is set to 60 DEG C ~ 80 DEG C, at the top layer of above-mentioned anode pole piece spraying soluble organic macromolecule substance solution, form soluble organic macromolecule material layer, again the pole piece after spraying is dried in vacuum drying chamber, obtain anode slice of lithium ion battery.
The preparation method of above-mentioned anode slice of lithium ion battery, preferred: the Spray painting tool used during described spraying is the Spray pen for art designer (such as HD-188K Spray pen for art designer) being connected to ventilation tracheae, use this Spray painting tool to spray back and forth, make the polymer layer being injected in anode pole piece surface be discontinuous spot distribution.
The preparation method of above-mentioned anode slice of lithium ion battery, preferred: described soluble organic macromolecule substance solution is polyimides (PI) solution, and the organic solvent in polyimide solution is at least one in 1-METHYLPYRROLIDONE (NMP), dimethylacetylamide (DMAc), dimethyl formamide (DMF), triethyl phosphate (TEP), metacresol; The concentration of described polyimide solution is 0.5 ~ 5wt%.Polyimide solution can intercept positive electrode at the PI layer that pole piece is formed and directly contact with HF in electrolyte, and the Co reduced in positive electrode dissolves, thus improves anode pole piece cycle performance under high voltages.In circulating battery process, the phase transformation that PI layer can also suppress positive electrode to occur because of intensification, thus the high rate performance of positive electrode under high temperature can be improved.
The preparation method of above-mentioned anode slice of lithium ion battery, preferred: the organic solvent in described polyimide solution is 1-METHYLPYRROLIDONE, and the concentration of polyimide solution is 2 ~ 4wt%.
The preparation method of above-mentioned anode slice of lithium ion battery; preferred: the concrete process for preparation of described polyimide solution comprises: under inert gas shielding; diamine monomer and dianhydride monomer are added in described organic solvent by certain mol proportion; be heated to 50 DEG C ~ 70 DEG C and stir formation mixed liquor; add catalyst, then be heated to 170 DEG C ~ 200 DEG C abundant polymerization reactions and form.
In the above-mentioned preferred preparation method of the present invention, by using Spray pen for art designer, soluble organic macromolecule substance solution (particularly preferably PI solution) is painted on anode pole piece surface, the PI solution being characterized in being ejected into positive electrode surface is discontinuous spot distribution, loose structure is formed after drying on hot plate, and easy to operate simple and easy.Polymer layer can not affect the contact between positive electrode and conductive agent, does not destroy original conductance path in pole piece, still keeps the conductance network configuration between positive electrode, thus can not affect the conduction velocity of ion and electronics.Polymer layer can reduce the decomposition of charged positive electrode particle surface electrolyte, can alleviate the change of particle volume in cyclic process, can reduce the triangular active force of positive electrode, binding agent and conductive agent, and then can prevent from forming gap between three.
As a total technical conceive, the present invention also provides a kind of lithium ion battery, comprises positive pole, negative pole, the barrier film preventing both positive and negative polarity contact short circuit and electrolyte, and the anode pole piece of described positive pole is the anode slice of lithium ion battery of the invention described above.
Compared with prior art, the invention has the advantages that: the surface uniform of anode slice of lithium ion battery of the present invention is coated with polymer layer, the continuous point-like spraying of spraying method right and wrong, organic substance macromolecule layer has loose structure after flash baking, this structure can not affect the transmission of lithium ion between positive electrode and electrolyte interface, thus can ensure lithium ion deviating from and embedding between both positive and negative polarity; Organic polymer layer can suppress battery positive electrode and electrolyte in charge and discharge process to react, and can eliminate the HF near pole piece in electrolyte, thus reduces positive electrode dissolving in the electrolytic solution; Organic polymer layer can make lithium ion battery carry out discharge and recharge under high voltage environment, maintains the stable of cathode material structure, thus improves charge and discharge cycles and the high rate performance of battery.In addition, the method preparing anode pole piece in the present invention is simple, easy to operate, and cost is lower.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the infrared spectrum of solubility PI test in the present invention.
Fig. 2 is embodiment 1 ~ 2 and the discharge cycles curve of comparative example at 4.6V, 0.5C/0.5C.
Fig. 3 is embodiment 1 and the rate discharge curves of comparative example at 4.5V.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
A kind of anode slice of lithium ion battery of the present invention, comprise collector and coating positive pole diaphragm on a current collector, positive pole diaphragm forms primarily of positive electrode active materials, conductive agent and binding agent, the top layer spraying polymer layer of positive pole diaphragm, the thickness of polymer layer is about 50nm; The main constituent of polymer layer is polyimides (PI), and this polymer layer is discontinuous spot distribution.The positive electrode active materials of the present embodiment is LiCoO
2, positive electrode active materials, conductive agent (acetylene black) are 94: 3: 3 with the proportioning of binding agent (poly-vinylidene).
The preparation method of the anode slice of lithium ion battery of above-mentioned the present embodiment, comprises the following steps:
(1) by D
50be about the positive electrode active materials LiCoO of 18 μm
2, conductive agent (acetylene black) and binding agent (poly-vinylidene) to mix in mass ratio at 94: 3: 3, add after in organic solvent 1-METHYLPYRROLIDONE (NMP) and repeatedly stir until evenly, obtain anode sizing agent; Subsequently anode sizing agent is coated in 20 μm of thick current collector aluminum foil, is placed on the lower 120 DEG C of oven dry of vacuum drying chamber, obtains anode pole piece;
(2) anode pole piece is placed on the heating plate of fume hood, the temperature of heating plate is set to 70 DEG C, at the top layer of above-mentioned anode pole piece spraying soluble polyimide (PI) solution, the Spray painting tool used during spraying is the HD-188K Spray pen for art designer being connected to ventilation tracheae, this Spray pen for art designer is used to spray back and forth, after NMP volatilization completely, form solubility PI sprayed coating, and make the PI sprayed coating being injected in anode pole piece surface be discontinuous spot distribution, again the pole piece after spraying is dried in 120 DEG C of vacuum drying chambers, obtain anode slice of lithium ion battery, after drying, the anode pole piece of PI spraying is stamped into the anode slice of lithium ion battery that diameter is 12mm.
The preparation of above-mentioned soluble polyimide (PI) solution comprises the following steps: at N
2under atmosphere, the proportioning of 1: 1: 2 is by octadecylamine, 2 in mass ratio, two [the 4-(-ammonia phenoxy base) phenyl] propane, 4 of 2-, the two phthalic anhydride (ODA, BAPP, ODPA) of 4 oxygen is blended in metacresol, be heated to 50 DEG C ~ 70 DEG C and stir formation mixed liquor, add benzoic acid as catalyst, then at N
2be heated to 180 DEG C under atmosphere and the 12h that refluxes, obtain PI macromolecule polymer solution.After question response terminates, PI macromolecule polymer solution is poured into cyclic washing in the mixed liquor of industrial alcohol and deionized water, thoroughly clean the metacresol in PI and benzoic acid, PI is positioned over vacuum drying chamber and keeps 24h to dry under 120 DEG C of conditions; Then the PI taking 2 ~ 4 parts of quality is dissolved in the NMP of 98 ~ 96 parts of quality, magnetic agitation 20min, is mixed with the PI solution (the present embodiment is particularly preferably the PI solution of 3%) that mass fraction is 2% ~ 4%.In the present embodiment, the infrared spectrum of solubility PI test as shown in Figure 1.As seen from Figure 1, about 1720cm in spectrogram
-1with 1780cm
-1place observes the characteristic peak of cyclic imide structure, not containing other high molecular polymers in provable PI.
Lithium ion battery negative electrode is that in Tianjin, fertile diameter is the circular metal lithium sheet of 16mm.
The anode slice of lithium ion battery of above-mentioned preparation, lithium ion battery negative electrode and barrier film (20 μm) are superimposed, add the electrolyte (LiPF of 1mol/L
6wherein nonaqueous solvents by ethylene carbonate, Merlon, methyl ethyl carbonate, fluorinated ethylene carbonate (EC, PC, EMC, FEC) forms and mass percent is followed successively by 25: 25: 44: 6), in the glove box being full of argon gas, be assembled into CR3032 type button cell.
Embodiment 2:
In the present embodiment the step of preparation process of lithium ion battery positive and negative electrode pole piece and lithium ion battery and technological parameter substantially the same manner as Example 1, its difference is only, the main constituent of the polymer layer in the present embodiment is Kynoar (PVDF), when spraying on the top layer of anode pole piece be select mass fraction be 2% ~ 4% soluble poly vinylidene solution, form PVDF sprayed coating at product surface after spraying, this coating is equally in discontinuous spot distribution.The Kynoar (PVDF) of 2 ~ 4 parts of quality is mainly dissolved in the NMP of 98 ~ 96 parts of quality by the preparation of this soluble poly vinylidene solution, magnetic agitation 20min, can be mixed with the PVDF solution (the present embodiment is particularly preferably the PVDF solution of 3%) that mass fraction is 2% ~ 4%.
Comparative example:
In this comparative example the step of preparation process of lithium ion battery negative electrode and lithium ion battery and technological parameter substantially the same manner as Example 1, its difference is only, common anode pole piece is used in this comparative example, but not the anode pole piece of spraying polymer layer, namely do not comprise the correlation step of preparation, spraying polymer layer in this comparative example yet.
Cycle performance of battery is tested:
With indigo plant electric battery test system, charge-discharge performance test is carried out to above-described embodiment 1 ~ 2 and comparative example, the CR3032 type button cell that each embodiment and comparative example obtain is loaded onto test cabinet, under 25 DEG C of environment, after within first week, being charged to 4.6V state with the charging current of 0.1C, put to cut-ff voltage 3.0V with the discharging current of 0.1C again, carry out charge-discharge performance test with 0.5C/0.5C again after 2nd week, its discharge cycles curve as shown in Figure 2.As can be seen from Figure 2, relative to anode pole piece conventional in comparative example, in embodiment 1 3% PI and embodiment 2 in 3% the anode pole piece that sprays of PVDF make the high voltage cycle performance after battery be improved significantly, the improvement effect of the anode pole piece of the PI spraying of 3% is better.
Battery high rate performance is tested:
With indigo plant electric battery test system, charge-discharge magnification performance test is carried out to embodiment 2 and comparative example 1, the battery that above-described embodiment and comparative example obtain is loaded onto test cabinet, after within the 1st week under 25 DEG C of environment, being charged to 4.5V state with the charging current of 0.1C, put to cut-ff voltage 3.0V with the discharging current of 0.1C again, within 2nd week, carry out charge-discharge test with 1C/1C, within 3rd week, carry out charge-discharge test with 1C/2C, within the 4th week, carry out charge-discharge test with 1C/5C, within the 5th week, carry out charge-discharge test with 1C/10C.The rate discharge curves that this test of Fig. 3 obtains, as can be seen from Figure 3, the high rate performance after the anode pole piece that in embodiment 1, the PI of 3% sprays makes battery compares ratio 1 remarkable lifting.
Therefore: the anode pole piece of solubility PI spraying, PI layer can not affect the contact between positive electrode and conductive agent, can not destroy original conductance path in pole piece, still keeps the conductance network configuration between positive electrode, thus can not affect the cycle performance of battery.PI layer can reduce the decomposition of charged positive electrode particle surface electrolyte, can alleviate the change of particle volume in cyclic process, can reduce the triangular active force of positive electrode, binding agent and conductive agent, and then can prevent from forming gap between three.The PI layer of pole piece can intercept positive electrode and directly contact with HF in electrolyte, and the Co reduced in positive electrode dissolves, thus improves battery cycle performance under high voltages.In battery charge and discharge process, the phase transformation that PI layer can suppress positive electrode to occur because of intensification, thus improve the high rate performance of positive electrode.
Claims (10)
1. an anode slice of lithium ion battery, comprise collector and coating positive pole diaphragm on a current collector, described positive pole diaphragm forms primarily of positive electrode active materials, conductive agent and binding agent, it is characterized in that: the top layer spraying polymer layer of described positive pole diaphragm, the thickness h≤100nm of described polymer layer; The main constituent of described polymer layer is at least one in polyimides, Kynoar, polytetrafluoroethylene, polyacrylonitrile.
2. anode slice of lithium ion battery as claimed in claim 1, it is characterized in that: the thickness h≤50nm of described polymer layer, described polymer layer is discontinuous spot distribution.
3. anode slice of lithium ion battery as claimed in claim 1, is characterized in that: described positive electrode active materials is LiCoO
2, LiNi
xco
ymn
(1-x-y)o
2, LiMn
2o
4, LiFePO
4in at least one, wherein y≤1, x+y≤1, the proportioning of described positive electrode active materials, conductive agent and binding agent is 94 ~ 96: 3 ~ 2: 3 ~ 2.
4. anode slice of lithium ion battery as claimed in claim 3, is characterized in that: described positive electrode active materials is LiCoO
2, and LiCoO
2d50>=5 μm; The proportioning of described positive electrode active materials, conductive agent and binding agent is 94: 3: 3; The main constituent of described polymer layer is polyimides.
5. the preparation method of anode slice of lithium ion battery according to any one of Claims 1 to 4, comprises the following steps:
(1) described positive electrode active materials, conductive agent, binding agent are mixed in mass ratio, add after in organic solvent and repeatedly stir until evenly, obtain anode sizing agent; Subsequently by anode sizing agent coating on a current collector, dry under being placed on vacuum drying chamber, obtain anode pole piece;
(2) anode pole piece is placed on the heating plate of fume hood, the temperature of heating plate is set to 60 DEG C ~ 80 DEG C, at the top layer of above-mentioned anode pole piece spraying soluble organic macromolecule substance solution, form soluble organic macromolecule material layer, again the pole piece after spraying is dried in vacuum drying chamber, obtain anode slice of lithium ion battery.
6. the preparation method of anode slice of lithium ion battery as claimed in claim 5, it is characterized in that: the Spray painting tool used during described spraying is the Spray pen for art designer being connected to ventilation tracheae, use this Spray painting tool to spray back and forth, make the polymer layer being injected in anode pole piece surface be discontinuous spot distribution.
7. the preparation method of anode slice of lithium ion battery as claimed in claim 5, it is characterized in that: described soluble organic macromolecule substance solution is polyimide solution, and the organic solvent in polyimide solution is at least one in 1-METHYLPYRROLIDONE, dimethylacetylamide, dimethyl formamide, triethyl phosphate, metacresol; The concentration of described polyimide solution is 0.5 ~ 5wt%.
8. the preparation method of anode slice of lithium ion battery as claimed in claim 7, it is characterized in that: the organic solvent in described polyimide solution is 1-METHYLPYRROLIDONE, and the concentration of polyimide solution is 2 ~ 4wt%.
9. the preparation method of anode slice of lithium ion battery as described in claim 7 or 8; it is characterized in that; the concrete process for preparation of described polyimide solution comprises: under inert gas shielding; diamine monomer and dianhydride monomer are added in described organic solvent by certain mol proportion; be heated to 50 DEG C ~ 70 DEG C and stir formation mixed liquor; add catalyst, then be heated to 170 DEG C ~ 200 DEG C abundant polymerization reactions and form.
10. a lithium ion battery, comprises positive pole, negative pole, the barrier film preventing both positive and negative polarity contact short circuit and electrolyte, it is characterized in that: anode pole piece anode slice of lithium ion battery according to any one of Claims 1 to 4 of described positive pole.
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| CN105118958A (en) * | 2015-08-13 | 2015-12-02 | 深圳市三讯电子有限公司 | Positive electrode plate and preparing method thereof and lithium ion battery |
| CN105226235A (en) * | 2015-10-19 | 2016-01-06 | 湖南杉杉新能源有限公司 | Lithium ion cell positive that a kind of gelatin polymer is coated and preparation method thereof |
| JP2018163877A (en) * | 2017-03-24 | 2018-10-18 | ユニチカ株式会社 | Binder solution and coating liquid |
| CN109713214A (en) * | 2018-12-03 | 2019-05-03 | 银隆新能源股份有限公司 | A kind of electrode slice and lithium ion battery of lithium ion battery |
| CN109994708A (en) * | 2017-12-29 | 2019-07-09 | 宁德时代新能源科技股份有限公司 | Negative pole piece, preparation method thereof and secondary battery |
| CN109994707A (en) * | 2017-12-29 | 2019-07-09 | 宁德时代新能源科技股份有限公司 | Positive plate, preparation method thereof and battery |
| CN111509189A (en) * | 2019-01-30 | 2020-08-07 | 广州汽车集团股份有限公司 | Positive pole piece and lithium ion battery |
| CN112687839A (en) * | 2020-12-24 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Pole piece, preparation method thereof and lithium ion battery |
| CN113130843A (en) * | 2021-04-10 | 2021-07-16 | 中国科学院福建物质结构研究所 | Electrode and preparation method thereof |
| CN113540392A (en) * | 2020-04-17 | 2021-10-22 | 北京化工大学 | Integrated high-safety composite pole piece for lithium ion battery and preparation method thereof |
| CN114023967A (en) * | 2021-10-29 | 2022-02-08 | 蜂巢能源科技有限公司 | Positive pole piece and preparation method and application thereof |
| CN114725482A (en) * | 2022-03-16 | 2022-07-08 | 江苏环峰电工材料有限公司 | Rechargeable battery and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102881861A (en) * | 2012-09-26 | 2013-01-16 | 中南大学 | High-temperature lithium ion battery anode slice |
| CN103828092A (en) * | 2012-04-10 | 2014-05-28 | 株式会社Lg化学 | Electrode including porous coating layer, method for manufacturing same, and electrochemical device including same |
| CN104466191A (en) * | 2013-05-07 | 2015-03-25 | 株式会社Lg化学 | Electrode for secondary battery, method for manufacturing same, and secondary battery and cable-type secondary battery comprising same |
-
2015
- 2015-04-13 CN CN201510171935.0A patent/CN104766946B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103828092A (en) * | 2012-04-10 | 2014-05-28 | 株式会社Lg化学 | Electrode including porous coating layer, method for manufacturing same, and electrochemical device including same |
| CN102881861A (en) * | 2012-09-26 | 2013-01-16 | 中南大学 | High-temperature lithium ion battery anode slice |
| CN104466191A (en) * | 2013-05-07 | 2015-03-25 | 株式会社Lg化学 | Electrode for secondary battery, method for manufacturing same, and secondary battery and cable-type secondary battery comprising same |
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| CN105226235A (en) * | 2015-10-19 | 2016-01-06 | 湖南杉杉新能源有限公司 | Lithium ion cell positive that a kind of gelatin polymer is coated and preparation method thereof |
| CN105226235B (en) * | 2015-10-19 | 2018-06-12 | 湖南杉杉新能源有限公司 | A kind of lithium ion cell positive of gelatin polymer cladding and preparation method thereof |
| JP2018163877A (en) * | 2017-03-24 | 2018-10-18 | ユニチカ株式会社 | Binder solution and coating liquid |
| CN109994707B (en) * | 2017-12-29 | 2021-09-21 | 宁德时代新能源科技股份有限公司 | Positive plate, preparation method thereof and battery |
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| CN109994708B (en) * | 2017-12-29 | 2021-07-13 | 宁德时代新能源科技股份有限公司 | Negative pole piece, preparation method thereof and secondary battery |
| CN109713214A (en) * | 2018-12-03 | 2019-05-03 | 银隆新能源股份有限公司 | A kind of electrode slice and lithium ion battery of lithium ion battery |
| CN111509189A (en) * | 2019-01-30 | 2020-08-07 | 广州汽车集团股份有限公司 | Positive pole piece and lithium ion battery |
| CN113540392A (en) * | 2020-04-17 | 2021-10-22 | 北京化工大学 | Integrated high-safety composite pole piece for lithium ion battery and preparation method thereof |
| CN112687839A (en) * | 2020-12-24 | 2021-04-20 | 惠州亿纬锂能股份有限公司 | Pole piece, preparation method thereof and lithium ion battery |
| CN113130843A (en) * | 2021-04-10 | 2021-07-16 | 中国科学院福建物质结构研究所 | Electrode and preparation method thereof |
| CN113130843B (en) * | 2021-04-10 | 2022-06-10 | 中国科学院福建物质结构研究所 | Electrode and preparation method thereof |
| CN114023967A (en) * | 2021-10-29 | 2022-02-08 | 蜂巢能源科技有限公司 | Positive pole piece and preparation method and application thereof |
| CN114725482A (en) * | 2022-03-16 | 2022-07-08 | 江苏环峰电工材料有限公司 | Rechargeable battery and application thereof |
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Address after: 410000 No. 166, Jinzhou Avenue East, Jinzhou new area, Ningxiang, Changsha City, Hunan Province Patentee after: BASF Shanshan battery material (Ningxiang) Co.,Ltd. Address before: 410000 No. 166, Jinzhou Avenue East, Jinzhou new area, Ningxiang, Changsha City, Hunan Province Patentee before: HUNAN SHANSHAN NEW ENERGY Co.,Ltd. |