CN104201326A - Pole piece of lithium ion secondary battery - Google Patents

Pole piece of lithium ion secondary battery Download PDF

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Publication number
CN104201326A
CN104201326A CN201410381372.3A CN201410381372A CN104201326A CN 104201326 A CN104201326 A CN 104201326A CN 201410381372 A CN201410381372 A CN 201410381372A CN 104201326 A CN104201326 A CN 104201326A
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CN
China
Prior art keywords
pole piece
lithium
acetylene black
ion secondary
secondary battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410381372.3A
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Chinese (zh)
Inventor
龚明
侯峰
林斯辉
张光荣
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JIANGXI CHANG HE NEW BATTERY CO Ltd
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JIANGXI CHANG HE NEW BATTERY CO Ltd
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Application filed by JIANGXI CHANG HE NEW BATTERY CO Ltd filed Critical JIANGXI CHANG HE NEW BATTERY CO Ltd
Priority to CN201410381372.3A priority Critical patent/CN104201326A/en
Publication of CN104201326A publication Critical patent/CN104201326A/en
Pending legal-status Critical Current

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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • H01M4/622—Binders being polymers
    • H01M4/623—Binders being polymers fluorinated polymers
    • 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
    • H01M4/625—Carbon or graphite
    • 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 pole piece of a lithium ion secondary battery, which is classified as a pole piece of a positive pole and a pole piece of a negative pole. The pole piece of the positive pole is prepared from 73.0%-75.5% of lithium nickel cobalt manganese oxide, 17.0%-20.0% of lithium manganite, 4.25%-4.75% of acetylene black (SP, the particle size is 40-45nm), 2.75%-3.25% of PVDF (polyvinylidene fluoride) according to the formulation ratio, wherein lithium nickel cobalt manganese oxide is prepared from three powder including lithium nickel oxide, lithium manganite and lithium cobaltate in the ratio of 1 to 1 to 1. The pole piece of the negative pole is prepared from 87.5%-90.5% of graphite, 2.75%-3.25% of acetylene black (SP, the particle size is 40-45nm), 2.75%-3.25% of acetylene black A (SP, the particle size is 30-35nm), 4.5%-5.5% of PVDF (polyvinylidene fluoride) and 0.09%-0.11% of oxalic acid according to the formulation ratio. By adopting the pole piece of the lithium ion secondary battery, the maximum momentary discharge current of a battery core achieves 30C, and reaches the advanced level in the same industry.

Description

A kind of lithium ion secondary battery pole piece
Technical field
The present invention relates to a kind of lithium ion secondary battery pole piece, belong to lithium ion battery field.
Background technology
Large high rate performance lithium rechargeable battery is widely used in mine lamp, electric tool and some main equipments, particularly be used in military aspect, the portable equipment of tactics (as equipment such as communication, commander, scouting and location) is core power supply unit mainly with lithium ion battery, can meet the equipment need for electricity under multiple use pattern.
Both at home and abroad the research of large doubly forthright lithium rechargeable battery is also constantly heated up, the design that wherein changes inside battery is the main path that improves high rate discharge for lithium ion battery, increase the internal resistance that the lug quantity of welding on electrode plates can reduce battery, improve the discharge platform of battery, electrode active material and conductive agent, the proportioning of binding agent, the surface density of electrode slice has a great impact the high-rate discharge ability tool of lithium ion battery, colleague's lithium rechargeable battery fails to accomplish good ratio optimization to pole piece material at present, continuous discharge electric current is between 10C-15C, maximum instantaneous discharging current is between 20-25C, discharge-rate is general.
Summary of the invention
Object of the present invention aims to provide a kind of lithium ion secondary battery pole piece, makes the maximum continuous discharge electric current of battery core reach 20C, and maximum instantaneous discharging current reaches 30C, improves battery core consistency and fail safe.
For achieving the above object, lithium ion secondary battery pole piece of the present invention, be divided into anode pole piece and cathode pole piece, anode pole piece is by nickle cobalt lithium manganate 73.0%～75.5%, LiMn2O4 17.0%～20.0%, acetylene black (SP, particle diameter is 40-45nm) 4.25%～4.75%, PVDF (polyvinylidene fluoride) 2.75%～3.25% is formulated, nickle cobalt lithium manganate is by lithium nickelate: LiMn2O4: the ratio of cobalt acid lithium is that 1: 1: 1 three kinds of powder is formulated, cathode pole piece is by graphite 87.5%～90.5%, acetylene black (SP, particle diameter is 40-45nm) 2.75%～3.25%, acetylene black A (SP, particle diameter is 30-35nm) 2.75%～3.25%, PVDF (polyvinylidene fluoride) 4.5%～5.5%, oxalic acid 0.09%～0.11% is formulated.
Lithium ion secondary battery pole piece of the present invention compared with prior art has following excellent effect.
Adopt lithium ion secondary battery pole piece of the present invention, make the maximum instantaneous discharging current of battery core reach 30C, in advanced level of the same trade, this anode formula design, optimized the ratio of positive electrode active materials, conductive agent, binding agent, in the situation that increasing conductive agent content, anode pole piece has good adhesion, the phenomenon that there will not be to fall material at film-making and winding process, has improved battery core consistency and fail safe; This cathode formula has been optimized the ratio of negative active core-shell material, conductive agent, binding agent, in the situation that increasing conductive agent content, cathode pole piece has good adhesion, there will not be to fall the phenomenon of material at film-making and winding process, has improved battery core consistency and fail safe.
Embodiment
Below lithium ion secondary battery pole piece of the present invention is described in further detail.
Lithium ion secondary battery pole piece of the present invention is divided into anode pole piece and cathode pole piece, anode pole piece is by nickle cobalt lithium manganate 73.0%～75.5%, LiMn2O4 17.0%～20.0%, acetylene black (SP, particle diameter is 40-45nm) 4.25%～4.75%, PVDF (polyvinylidene fluoride) 2.75%～3.25% is formulated, nickle cobalt lithium manganate is by lithium nickelate: LiMn2O4: the ratio of cobalt acid lithium is that 1: 1: 1 three kinds of powder is formulated, cathode pole piece is by graphite 87.5%～90.5%, acetylene black (SP, particle diameter is 40-45nm) 2.75%～3.25%, acetylene black A (SP, particle diameter is 30-35nm) 2.75%～3.25%, PVDF (polyvinylidene fluoride) 4.5%～5.5%, oxalic acid 0.09%～0.11% is formulated.
Lithium ion secondary battery pole piece of the present invention is divided into anode pole piece and cathode pole piece, the outfit of anode pole piece and cathode pole piece is all weight percentage, get the raw materials ready by formulation ratio of the present invention, production technology is made routinely, then is coated in respectively on plus plate current-collecting body and negative current collector.
Pole piece manufacturing process comprises two parts: blending process and coating procedure.
Blending process:
Positive plate batching: whipping process and procedure parameter control are described,
1. add the PVDF of nmp solvent and 2.75%～3.25% ratio to make glue, require stirring machine revolution rotating speed to be: 15-45rpm, rotation rotating speed is: 800-2000rpm, the time is: 1h;
2. test gelatin viscosity with viscosimeter;
3. add the acetylene black of 4.25%～4.75% ratio, require stirring machine revolution rotating speed to be: 15-45rpm, rotation rotating speed is: 800-2000rpm, the time is: 1h;
4. add the LiMn2O4 of 17.0%～20.0% ratio, require stirring machine revolution rotating speed to be: 45rpm, rotation rotating speed is: 800-2000rpm, the time is: 2h;
5. add the nickle cobalt lithium manganate of 73.0%～75.5% ratio, require stirring machine revolution rotating speed to be: 15-45rpm, rotation rotating speed is: 800-2000rpm, the time is: 2h;
6. by viscosimeter testing size viscosity, range of viscosities 1500-6000mPa.s, if viscosity, not in scope, adds NMP to regulate;
As slurry viscosity in claimed range slurry sieve and proceed to coating operation, be applied on the aluminium foil of 10-30um, baking is dry, baking temperature 65-130 DEG C becomes positive plate after baking is dry.
Negative plate batching: describe whipping process and procedure parameter control, (NMP is solvent)
1. add the PVDF of nmp solvent and 4.5%～5.5% ratio to make glue, require stirring machine revolution rotating speed to be: 15-45rpm rpm, rotation rotating speed is: 800-2000rpm, the time is: 1h;
2. test gelatin viscosity with viscosimeter;
3. add the acetylene black of 2.75%～3.25% ratio, require stirring machine revolution rotating speed to be: 15-45rpmrpm, rotation rotating speed is: 800-2000rpm, the time is: 1h;
4. add the acetylene black A of 2.75%～3.25% ratio, require stirring machine revolution rotating speed to be: 15-45rpmrpm, rotation rotating speed is: 800-2000rpm, the time is: 1h;
5. add the graphite of 87.5%～90.5% ratio, require stirring machine revolution rotating speed to be: 15-45rpmrpm, rotation rotating speed is: 800-2000rpm, the time is: 2h;
6. add the oxalic acid of 0.09%～0.11% ratio, require stirring machine revolution rotating speed to be: 15-45rpmrpm, rotation rotating speed is: 800-2000rpm rpm, the time is: 1h;
7. by viscosimeter testing size viscosity, range of viscosities 1500-6000mPa.s, if viscosity, not in scope, adds NMP to regulate;
8. be applied on the Copper Foil of 8-20um, baking is dry, and baking temperature 65-130 DEG C becomes negative plate after baking is dry.
Acetylene black during by calcium carbide route or naphtha (raw gasoline) pyrolysis manufacture gas decompose more than 99% acetylene of the refining purity obtaining, the carbon black obtaining after continuous pyrolysis.

Claims (1)

1. a lithium ion secondary battery pole piece, be divided into anode pole piece and cathode pole piece, it is characterized in that anode pole piece is by nickle cobalt lithium manganate 73.0%～75.5%, LiMn2O4 17.0%～20.0%, acetylene black (SP, particle diameter is 40-45nm) 4.25%～4.75%, PVDF (polyvinylidene fluoride) 2.75%～3.25% is formulated, nickle cobalt lithium manganate is by lithium nickelate: LiMn2O4: the ratio of cobalt acid lithium is that 1: 1: 1 three kinds of powder is formulated, cathode pole piece is by graphite 87.5%～90.5%, acetylene black (SP, particle diameter is 40-45nm) 2.75%～3.25%, acetylene black A (SP, particle diameter is 30-35nm) 2.75%～3.25%, PVDF (polyvinylidene fluoride) 4.5%～5.5%, oxalic acid 0.09%～0.11% is formulated.
CN201410381372.3A 2014-07-29 2014-07-29 Pole piece of lithium ion secondary battery Pending CN104201326A (en)

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Application Number Priority Date Filing Date Title
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868114A (en) * 2015-04-06 2015-08-26 江苏菲思特新能源有限公司 Preparation method of nickel-rich concentration gradient nickel-cobalt-manganese anode material with low acidity or alkalinity and high processability
CN106129389A (en) * 2016-09-29 2016-11-16 柳州申通汽车科技有限公司 The preparation method of new energy car battery pole piece
CN106159245A (en) * 2016-09-29 2016-11-23 柳州申通汽车科技有限公司 A kind of preparation method of graphene battery negative plate
CN106328897A (en) * 2016-09-29 2017-01-11 柳州申通汽车科技有限公司 Preparation method of composite negative electrode material for automobile battery
CN107819108A (en) * 2017-11-06 2018-03-20 贵州省铜仁华迪斯新能源有限公司 Ternary electrode slurry, ternary electrode piece and preparation method
CN111211304A (en) * 2020-01-13 2020-05-29 湖南丰源业翔晶科新能源股份有限公司 Long-cycle lithium ion battery and composite positive electrode active material, positive electrode slurry and positive electrode thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918731A (en) * 2004-02-07 2007-02-21 株式会社Lg化学 Electrode additives coated with electro conductive material and lithium secondary comprising the same
CN101685878A (en) * 2008-09-27 2010-03-31 深圳市比克电池有限公司 Preparation method of polymer lithium ion battery
US20130040201A1 (en) * 2010-03-03 2013-02-14 Arumugam Manthiram High capacity layered oxide cathods with enhanced rate capability

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918731A (en) * 2004-02-07 2007-02-21 株式会社Lg化学 Electrode additives coated with electro conductive material and lithium secondary comprising the same
CN101685878A (en) * 2008-09-27 2010-03-31 深圳市比克电池有限公司 Preparation method of polymer lithium ion battery
US20130040201A1 (en) * 2010-03-03 2013-02-14 Arumugam Manthiram High capacity layered oxide cathods with enhanced rate capability

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868114A (en) * 2015-04-06 2015-08-26 江苏菲思特新能源有限公司 Preparation method of nickel-rich concentration gradient nickel-cobalt-manganese anode material with low acidity or alkalinity and high processability
CN106129389A (en) * 2016-09-29 2016-11-16 柳州申通汽车科技有限公司 The preparation method of new energy car battery pole piece
CN106159245A (en) * 2016-09-29 2016-11-23 柳州申通汽车科技有限公司 A kind of preparation method of graphene battery negative plate
CN106328897A (en) * 2016-09-29 2017-01-11 柳州申通汽车科技有限公司 Preparation method of composite negative electrode material for automobile battery
CN107819108A (en) * 2017-11-06 2018-03-20 贵州省铜仁华迪斯新能源有限公司 Ternary electrode slurry, ternary electrode piece and preparation method
CN111211304A (en) * 2020-01-13 2020-05-29 湖南丰源业翔晶科新能源股份有限公司 Long-cycle lithium ion battery and composite positive electrode active material, positive electrode slurry and positive electrode thereof
CN111211304B (en) * 2020-01-13 2021-09-03 湖南丰源业翔晶科新能源股份有限公司 Long-cycle lithium ion battery and composite positive electrode active material, positive electrode slurry and positive electrode thereof

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Application publication date: 20141210