CN103606700A - Lithium ion battery with good charge and discharge performance - Google Patents
Lithium ion battery with good charge and discharge performance Download PDFInfo
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- CN103606700A CN103606700A CN201310577090.6A CN201310577090A CN103606700A CN 103606700 A CN103606700 A CN 103606700A CN 201310577090 A CN201310577090 A CN 201310577090A CN 103606700 A CN103606700 A CN 103606700A
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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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
- 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
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- 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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a lithium ion battery with good charge and discharge performance. The lithium ion battery comprises a positive plate, a negative plate, as well as a membrane barrier and an electrolyte which are arranged between the positive plate and the negative plate, wherein a positive electrode adopts a ternary positive electrode material containing nickel cobalt manganese, a negative electrode adopts a porous graphite flake material. The lithium ion battery with good charge and discharge performance provided by the invention has the characteristics that not only can atomic-level uniform mixing of the three metals be realized but also the ternary positive electrode material is fine in consistency, and the problems of high production costs of existing porous carbon materials, complex devices required by reaction and low discharge specific capacity are solved.
Description
Technical field
The present invention relates to battery, be specifically related to the lithium ion battery that a kind of charge-discharge performance is good.
Background technology
At present, in Chinese or global energy resource structure, coal, oil, natural gas primary energy account for more than 90%, and its reserves only supply exploitation about 50 years, and therefore developing new forms of energy must become the grand strategy industry of immuning from the economic downturn, create employment opportunities, seize future development commanding elevation.In the new forms of energy systems such as solar energy, wind energy, nuclear energy, lithium ion battery because its energy density is high, power density is high, good cycle, environmental friendliness, structure diversification and the excellent specific property such as cheap become the first-selected power supply of the walkie electronic apparatus such as video camera, mobile phone, notebook computer, are also the ideal sources of future space technology and high-end energy-storage system.
The positive electrode that lithium ion battery adopts at present mainly contains cobalt acid lithium, LiFePO4, LiMn2O4 and tertiary cathode material etc.Tertiary cathode material has that specific capacity is high, Heat stability is good, the advantage such as cheap, be lithium ion battery produce can substituting cobalt acid lithium material in a kind of cell positive material of tool potentiality, in power fields such as electric motor car, electric tools, there is good application prospect.Although at present nickel, cobalt, manganese tertiary cathode material gram volume are high, tap density is low, and volume and capacity ratio is little, and adding multicomponent transition metal has increased the inhomogeneity difficulty of chemical composition in building-up process.Therefore, preparation high-performance, high-tap density nickel, cobalt, manganese tertiary cathode material become the key problem in technology of the industrialization of this system positive electrode.And porous graphite sheet layer material has the advantages such as stable physicochemical properties, larger specific area, cheap raw material and simple preparation method; Therefore,, in order to explore the height of its specific capacity that is applied to lithium ion battery and the length of cycle life, be necessary to be applied to lithium ion battery negative material.
Summary of the invention
The object of the invention is the defect for above-mentioned prior art, the lithium ion battery that a kind of charge-discharge performance is good is provided, there is high density, the advantage that charge-discharge performance is good and specific volume is high.
Object of the present invention can be achieved through the following technical solutions:
The lithium ion battery that charge-discharge performance is good, comprises positive plate, negative plate and is placed in barrier film and the electrolyte between positive and negative plate, the described anodal nickel-cobalt-manganese ternary positive electrode that adopts, and described negative pole adopts porous graphite sheet material.
Nickel-cobalt-manganese ternary positive electrode chemical formula is Li
1+z(Ni
1-x-yco
xmn
y) O
20≤z≤0.15 wherein, 0.1≤x≤1/3,0.1≤y≤0.4.Its crystal grain is spherical or class ball-type, and granularity D50 is 13~57 μ m, and tap density is 2.3~2.7g/cm
3, specific area is 0.05~0.2m
2/ g.
Metallic nickel, cobalt, Mn mixture are having under inert gas shielding condition; carry out high-temperature fusion; after melting, carry out atomization granulation; after granulation, under temperature is the condition of 400~1000 ℃, be oxidized 0.5~11 hour and obtain nickel cobalt manganese alloy oxide; this oxide and lithium compound are pressed metal element content mol ratio for (Ni+Co+Mn): Li=1:(1+z); 0≤z≤0.15 wherein, after mixing 600~1000 ℃ of roasting temperatures 3~16 hours.
The making of described anodal employing nickel-cobalt-manganese ternary positive electrode comprises the following steps:
A, by metallic nickel, cobalt, manganese, according to mol ratio, be the ratio mix of (1-x-y): x:y, 0≤x≤1 wherein, 0≤y≤1,0<x+y≤1, compound is warming up to the above temperature melting of alloy melting point having under inert gas shielding condition, after melting, carry out atomization granulation, obtain nickel-cobalt-manganese alloy powder;
B, by alloyed powder obtained in the previous step, in temperature, be to be oxidized 0.5~11 hour under the condition of 400~1000 ℃, obtain nickel cobalt manganese alloy oxide;
C, nickel cobalt manganese alloy oxide obtained in the previous step and lithium compound are pressed to metal element content mol ratio for (Ni+Co+Mn): Li=1:(1+z), 0≤z≤0.15 wherein, after mixing, 600~1050 ℃ of roasting temperatures 3~16 hours, obtain lithium ion battery tertiary cathode material.
Described lithium compound can be containing one or more mixing in the oxide of lithium, halide, hydroxide, carbonate, nitrate, oxalates, acetate, citrate.
The making of described negative pole porous graphite sheet material comprises the following steps:
A, under stirring condition, graphite is joined in the mixed acid solution of sulfuric acid and nitric acid, controlling temperature is 15 ℃~55 ℃, keeps 0.5h~2h, then centrifugation, be washed to acidity, dehydrate, then controlling microwave power is 3kW again, keeps 30s, obtain expanded graphite, allowance for expansion is 150mL/g~260mL/g, and wherein the mass ratio of graphite and mixed acid is 1: 2~6, and the mass ratio of sulfuric acid and nitric acid is 2~4: 1;
B, expanded graphite prepared by previous step join in solvent, solvent is one or more the mixing in water, ethanol and ethylene glycol, add again surfactant, adopt ultrasonic method or heating paddling process evenly to mix, obtain mixture, wherein, the mass ratio of expanded graphite and solvent is 2: 25~100;
C, pore creating material is dissolved in solvent, add again mixture obtained in the previous step, stirring at room 4h~8h, control mixing speed is 300r/min~400r/min, then in temperature, be dry under 60 ℃~80 ℃ conditions, obtain porous presoma, wherein the mass ratio of pore creating material and solvent is 1: 5~30, and in mixture, the mass ratio of expanded graphite and pore creating material is 1: 5~30;
D, porous presoma prepared by previous step are under inert gas atmosphere condition, inert gas atmosphere flow is 120mL/min~400mL/min, be warming up to 700 ℃~1100 ℃, control programming rate and be 2 ℃/min~20 ℃/min, porous presoma is heat-treated, and heat treatment time is 1h~5h, more extremely neutral with acid solution and distilled water washing, under the bake out temperature of 60 ℃~85 ℃, dry, obtain the porous stone ink sheet of the super electric negative pole of lithium electricity.
Described surfactant is one or more in softex kw, dodecyl sodium sulfate, lauryl sodium sulfate, cetyl benzene sulfonic acid sodium salt, sodium stearyl sulfate or polydiene propyl-dimethyl amine ammonium chloride.
Described pore creating material is one or more the mixing in zinc acetate, zinc chloride, potassium hydroxide, NaOH, calcium oxide, calcium carbonate, calcium hydroxide and potash.
Beneficial effect of the present invention: not only realized the even mixing of three kinds of metallic atom levels, and this tertiary cathode material high conformity, positive electrode directly adopts nickel, cobalt, manganese metal as raw material, by high-temperature atomizing, make uniform alloy powder, be oxidized again and produce with the method for lithium compound roasting lithiumation, improve to the full extent the density of product, the present invention also solves that existing porous carbon materials production cost is high, reaction equipment needed thereby is complicated, the problem that specific discharge capacity is low.
Embodiment
Below by embodiment, the present invention is described in detail.
For positive electrode, adopt following steps:
Step 1: the ratio mix that is 2:1:2 according to mol ratio by metallic nickel, cobalt, manganese; compound is having under argon shield condition; metal liquid in induction furnace after fusing, melting is poured in insulation crucible; send into mozzle and nozzle; metal flow after melting is by the atomization of high pressure argon gas stream institute; metal dust after atomization solidifies in atomisation tower, sedimentation, finally fall into and receive powder tank and collect, and obtains nickel-cobalt-manganese alloy powder.This alloyed powder reaches the even mixing of atomic level on composition, and powder particle is that regular spherical, apparent density reach 5.10g/cm
3, tap density reaches 5.60g/cm
3.
Step 2: alloyed powder obtained in the previous step is oxidized in oxidation furnace, and oxidizing temperature is 900 ℃, and oxidization time is 1 hour, keeps alloyed powder oxidized calcining under dynamic situation, is heated evenly, and without hardening phenomenon, obtains nickel cobalt manganese alloy oxide.This alloy oxidation powder has been inherited the feature of alloyed powder high density and high sphericity, makes spherome surface become loose porous with the even combination of oxygen simultaneously, is conducive to after-stage and lithium compound and carries out lithiation.
Step 3: be (Ni+Co+Mn) with lithium hydroxide by metal element content mol ratio by nickel cobalt manganese alloy oxide obtained in the previous step: evenly mix in Li=1:1.1 batch mixer, mixed material through 900 ℃ of roasting temperatures 10 hours, obtains lithium ion battery tertiary cathode material Li at high temperature furnace
1.1(Ni
0.5co
0.2mn
0.3) O
2.Pattern and the particle diameter of product are further controlled, and resulting materials granularity D50 is 50 μ m, and tap density is 2.7g/cm
3, specific area is 0.10m
2/ g.
With resulting materials, make battery anode slice, manufacturing process for positive plate is as follows: the tertiary cathode material that the present embodiment is obtained and conductive agent acetylene black, binding agent polyvinylidene fluoride in mass ratio 8:1:1 mix, add appropriate organic solvent 1-METHYLPYRROLIDONE, in agate mortar, grind even, form the colloidal mixture of thickness, then be uniformly coated on the aluminium foil that 0.02mm is thick, be placed in the dry 12h of 120 ℃ of vacuum drying chambers.Barrier film is used tri-layers of micro-pore composite diaphragm of Celgard2300PP/PE/PP, and negative pole adopts metal lithium sheet, and electrolyte adopts 1molL
-1liPF
6/ ethylene carbonate: dimethyl carbonate (1:1), to make 2025 type button cells and carry out battery performance test, battery is assembled in being full of the glove box of high-purity argon gas.The battery assembling carries out charge-discharge performance test with LAND battery test system.Charging/discharging voltage scope is 3~4.3V, and under the condition that charge-discharge magnification is 0.1C, material initial discharge capacity reaches 154.2mAh/g, and efficiency is 87% first.
Negative pole porous graphite sheet material is prepared according to following steps:
Step 1: under stirring condition, graphite is joined in the mixed acid solution of sulfuric acid and nitric acid, controlling temperature is 40 ℃, keep 1.3h, then centrifugation, is washed to acidity, dehydrate again, then controlling microwave power is 3kW, keeps 30s, wherein the mass ratio of graphite and mixed acid is 1: 3, and the mass ratio of sulfuric acid and nitric acid is 3: 1;
Step 2: 0.1g expanded graphite prepared by previous step joins in water 30ml, then add 0.5g dodecyl sodium sulfate, adopt ultrasonic method evenly to mix, obtain mixture;
Step 3: 0.5g zinc acetate and zinc chloride mixture are dissolved in 30ml water, add again mixture obtained in the previous step, stirring at room 5h, control mixing speed is 300r/min, then in temperature, be dry under 75 ℃ of conditions, obtain porous presoma, in mixture, the mass ratio of expanded graphite and zinc acetate and zinc chloride mixture is 1: 5;
Step 4: porous presoma prepared by step 3 is under inert gas atmosphere condition, and inert gas atmosphere flow is 300mL/min, is warming up to 900 ℃, and controlling programming rate is 7 ℃/min, and porous presoma is heat-treated, and heat treatment time is 3h; Extremely neutral with acid solution and distilled water washing again, acid solution is that mass concentration is 5% hydrochloric acid solution, and bake out temperature is 80 ℃, obtains the porous stone ink sheet of the super electric negative pole of lithium electricity.
It is raw material that present embodiment adopts cheap graphite powder, recycling low-cost reagent modifies it, by chemical means, carry out pore-creating, and then to have made specific area be 400~1000 times of large porous stone ink sheets of graphite, by controlling activating reagent and the mass ratio of expanded graphite and the size that activation temperature is carried out control hole, and then determine the size of lithium ion battery specific discharge capacity under the condition of the two different quality ratio.Porous graphite sheet material prepared by the present invention has the features such as good conductivity, thickness is controlled, hole dimension is even, specific area is larger, and its specific area is 300~700m
2/ g, is applied to its specific discharge capacity of lithium ion battery by this porous carbon and reaches 400~1000mAh/g, is its 4~5 times with take that battery that graphite is negative material compares.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technology people of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and specification, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (8)
1. the good lithium ion battery of charge-discharge performance, comprises positive plate, negative plate and is placed in barrier film and the electrolyte between positive and negative plate, it is characterized in that: the described anodal manganese cobalt nickle triple positive electrode that adopts, described negative pole adopts porous graphite sheet material.
2. the good lithium ion battery of a kind of charge-discharge performance according to claim 1, is characterized in that: described manganese cobalt nickle triple positive electrode chemical formula is Li
1+z(Ni
1-x-yco
xmn
y) O
20≤z≤0.15 wherein, 0.1≤x≤1/3,0.1≤y≤0.4.Its crystal grain is spherical or class ball-type, and granularity D50 is 13~57 μ m, and tap density is 2.3~2.7g/cm
3, specific area is 0.05~0.2m
2/ g.
3. the good lithium ion battery of a kind of charge-discharge performance according to claim 2; it is characterized in that: manganese metal, cobalt, nickel compound are having under inert gas shielding condition; carry out high-temperature fusion; after melting, carry out atomization granulation; after granulation, under temperature is the condition of 400~1000 ℃, be oxidized 0.5~11 hour and obtain nickel cobalt manganese alloy oxide; this oxide and lithium compound are pressed metal element content mol ratio for (Ni+Co+Mn): Li=1:(1+z); 0≤z≤0.15 wherein, after mixing 600~1000 ℃ of roasting temperatures 3~16 hours.
4. the good lithium ion battery of a kind of charge-discharge performance according to claim 3, is characterized in that, the making of described anodal employing manganese cobalt nickle triple positive electrode comprises the following steps:
A, by manganese metal, cobalt, nickel, according to mol ratio, be the ratio mix of (1-x-y): x:y, 0≤x≤1 wherein, 0≤y≤1,0<x+y≤1, compound is warming up to the above temperature melting of alloy melting point having under inert gas shielding condition, after melting, carry out atomization granulation, obtain manganese cobalt-nickel alloy powder;
B, by alloyed powder obtained in the previous step, in temperature, be to be oxidized 0.5~11 hour under the condition of 400~1000 ℃, obtain manganese cobalt-nickel alloy oxide;
C, manganese cobalt-nickel alloy oxide obtained in the previous step and lithium compound are pressed to metal element content mol ratio for (Ni+Co+Mn): Li=1:(1+z), 0≤z≤0.15 wherein, after mixing, 600~1050 ℃ of roasting temperatures 3~16 hours, obtain lithium ion battery tertiary cathode material.
5. the good lithium ion battery of a kind of charge-discharge performance according to claim 4, is characterized in that: described lithium compound can be one or more mixing in oxide containing lithium, halide, hydroxide, carbonate, nitrate, oxalates, acetate, citrate.
6. the good lithium ion battery of a kind of charge-discharge performance according to claim 1, is characterized in that, the making of described negative pole porous graphite sheet material comprises the following steps:
A, under stirring condition, graphite is joined in the mixed acid solution of sulfuric acid and nitric acid, controlling temperature is 15 ℃~55 ℃, keeps 0.5h~2h, then centrifugation, be washed to acidity, dehydrate, then controlling microwave power is 3kW again, keeps 30s, obtain expanded graphite, allowance for expansion is 150mL/g~260mL/g, and wherein the mass ratio of graphite and mixed acid is 1: 2~6, and the mass ratio of sulfuric acid and nitric acid is 2~4: 1;
B, expanded graphite prepared by previous step join in solvent, solvent is one or more the mixing in water, ethanol and ethylene glycol, add again surfactant, adopt ultrasonic method or heating paddling process evenly to mix, obtain mixture, wherein, the mass ratio of expanded graphite and solvent is 2: 25~100;
C, pore creating material is dissolved in solvent, add again mixture obtained in the previous step, stirring at room 4h~8h, control mixing speed is 300r/min~400r/min, then in temperature, be dry under 60 ℃~80 ℃ conditions, obtain porous presoma, wherein the mass ratio of pore creating material and solvent is 1: 5~30, and in mixture, the mass ratio of expanded graphite and pore creating material is 1: 5~30;
D, porous presoma prepared by previous step are under inert gas atmosphere condition, inert gas atmosphere flow is 120mL/min~400mL/min, be warming up to 700 ℃~1100 ℃, control programming rate and be 2 ℃/min~20 ℃/min, porous presoma is heat-treated, and heat treatment time is 1h~5h, more extremely neutral with acid solution and distilled water washing, under the bake out temperature of 60 ℃~85 ℃, dry, obtain the porous stone ink sheet of the super electric negative pole of lithium electricity.
7. a kind of lithium ion battery that easy specific capacity is high of manufacturing according to claim 6, is characterized in that: described surfactant is one or more in softex kw, dodecyl sodium sulfate, lauryl sodium sulfate, cetyl benzene sulfonic acid sodium salt, sodium stearyl sulfate or polydiene propyl-dimethyl amine ammonium chloride.
8. a kind of lithium ion battery that easy specific capacity is high of manufacturing according to claim 7, is characterized in that: described pore creating material is one or more the mixing in zinc acetate, zinc chloride, potassium hydroxide, NaOH, calcium oxide, calcium carbonate, calcium hydroxide and potash.
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Cited By (7)
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CN105789599A (en) * | 2016-02-02 | 2016-07-20 | 北京理工大学 | Method for preparing porous silicon cathode material by polyvinyl alcohol freezing-unfreezing crosslinked carbonization |
CN106654208A (en) * | 2016-12-21 | 2017-05-10 | 深圳市沃特玛电池有限公司 | Preparation method for negative electrode material of lithium iron phosphate battery |
CN108484327A (en) * | 2018-05-03 | 2018-09-04 | 合肥宸翊商贸有限公司 | A kind of preparation method of Water-retaining slow-release fertilizer |
CN109093126A (en) * | 2018-06-15 | 2018-12-28 | 桑顿新能源科技有限公司 | A kind of preparation method of manganese Metal powder and anode material for lithium-ion batteries |
CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
CN114204013A (en) * | 2021-12-15 | 2022-03-18 | 中南大学 | Direct repairing method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
CN114824438A (en) * | 2022-04-01 | 2022-07-29 | 宁波吉利罗佑发动机零部件有限公司 | Battery monomer, power battery, vehicle auxiliary battery and battery package |
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CN102290597A (en) * | 2011-08-01 | 2011-12-21 | 珠海市鹏辉电池有限公司 | Safe-type high-energy density lithium-ion battery |
CN103259018A (en) * | 2013-04-27 | 2013-08-21 | 黑龙江大学 | Preparation method of porous graphite flake applied to super-electric negative pole of lithium battery |
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CN102169990A (en) * | 2011-04-07 | 2011-08-31 | 先进储能材料国家工程研究中心有限责任公司 | Ternary cathode material and production method thereof |
CN102290597A (en) * | 2011-08-01 | 2011-12-21 | 珠海市鹏辉电池有限公司 | Safe-type high-energy density lithium-ion battery |
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Cited By (9)
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CN105789599A (en) * | 2016-02-02 | 2016-07-20 | 北京理工大学 | Method for preparing porous silicon cathode material by polyvinyl alcohol freezing-unfreezing crosslinked carbonization |
CN105789599B (en) * | 2016-02-02 | 2018-05-08 | 北京理工大学 | The method that polyvinyl alcohol freeze-thaw cross-linking carbonization prepares porous silicon negative material |
CN106654208A (en) * | 2016-12-21 | 2017-05-10 | 深圳市沃特玛电池有限公司 | Preparation method for negative electrode material of lithium iron phosphate battery |
CN108484327A (en) * | 2018-05-03 | 2018-09-04 | 合肥宸翊商贸有限公司 | A kind of preparation method of Water-retaining slow-release fertilizer |
CN109093126A (en) * | 2018-06-15 | 2018-12-28 | 桑顿新能源科技有限公司 | A kind of preparation method of manganese Metal powder and anode material for lithium-ion batteries |
CN114068923A (en) * | 2020-07-30 | 2022-02-18 | 湖南中科星城石墨有限公司 | Modification method of graphite and application of graphite in lithium ion battery |
CN114204013A (en) * | 2021-12-15 | 2022-03-18 | 中南大学 | Direct repairing method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
CN114204013B (en) * | 2021-12-15 | 2024-03-22 | 中南大学 | Direct repair method for waste ternary lithium battery positive electrode material and ternary positive electrode material prepared by same |
CN114824438A (en) * | 2022-04-01 | 2022-07-29 | 宁波吉利罗佑发动机零部件有限公司 | Battery monomer, power battery, vehicle auxiliary battery and battery package |
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