CN105470476A - Lithium ion battery negative electrode for reducing irreversible capacity loss and preparation method of lithium ion battery negative electrode - Google Patents

Lithium ion battery negative electrode for reducing irreversible capacity loss and preparation method of lithium ion battery negative electrode Download PDF

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Publication number
CN105470476A
CN105470476A CN201510730367.3A CN201510730367A CN105470476A CN 105470476 A CN105470476 A CN 105470476A CN 201510730367 A CN201510730367 A CN 201510730367A CN 105470476 A CN105470476 A CN 105470476A
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ion battery
lithium ion
negative electrode
irreversible capacity
capacity loss
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CN105470476B (en
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李凡群
苏文俊
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Wanxiang A123 Systems Asia Co Ltd
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Universal A 1 System Co Ltd
Wanxiang Group Corp
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium ion battery negative electrode for reducing irreversible capacity loss. The lithium ion battery negative electrode comprises a negative electrode current collector and a negative electrode paste, wherein the negative electrode paste is coated on the surface of the negative electrode current collector and comprises the following constituents based on mass: 25-45% of negative electrode active substance, 0.3-5% of conductive agent, 0.3-5% of binding agent, 0-2% of surfactant, 0.0001-0.01% of lithium salt and 50-70% of water, and the percentage sum of all constituents is 100%. With the lithium ion battery negative electrode disclosed by the invention, the irreversible capacity loss of the battery can be effectively reduced, and the energy density of the battery is improved. The invention also provides a preparation method of the lithium ion battery negative electrode for reducing the irreversible capacity loss. The process step is simple, and the method is high in operability, is easy to implement, and can be completely applied to industrial production of a lithium ion battery at a large scale.

Description

A kind of lithium ion battery negative reducing irreversible capacity loss and preparation method thereof
Technical field
The present invention relates to lithium ion battery preparing technical field, especially relate to a kind of lithium ion battery negative reducing irreversible capacity loss and preparation method thereof.
Background technology
Directly positive/negative plate is assembled together by barrier film in the manufacture process of lithium ion battery at present, after fluid injection activation, inevitably produces irreversible capacity loss.
The irreversible capacity loss of lithium ion battery is seen as a kind of build-in attribute of lithium ion battery by existing technical scheme, by forming SEI film, the loss portion capacity of battery, first charge-discharge irreversible capacity is increased, this has badly influenced giving full play to of the energy content of battery.At present, large quantity research shows, the SEI film that negative terminal surface is formed is the main cause of irreversible capacity loss.Dissimilar negative material irreversible loss percentage is slightly different, and in general have the negative material of high specific surface area, irreversible capacity loss is larger.Although at present can by Surface coating, improve the surface topography of negative pole particle own and shape, optimization electrolyte solvent composition and use the means such as film for additive to reduce irreversible capacity loss, but irreversible capacity loss percentage is still higher, as Delanium 10 ~ 15%, soft carbon 10 ~ 20% etc.
Such as, application publication number: CN103682347A, the Chinese patent of Shen Qing Publication day 2014.03.26 discloses a kind of composite lithium ion battery cathode material, and this composite lithium ion battery cathode material is mainly composed of the following components: needle-like coke powder, and percentage by weight is 30%-50%; Natural spherical plumbago powder, percentage by weight is 20%-30%; Isotropism coke powder, percentage by weight is 15%-25%; Pitch coke powder, percentage by weight is 10%-20%.The weak point of this negative pole is: can increase irreversible capacity when first charge-discharge, affects giving full play to of the energy content of battery.
Summary of the invention
The present invention is that the lithium ion battery negative in order to solve prior art can increase irreversible capacity when first charge-discharge, affect the problem given full play to of the energy content of battery, provide a kind of formulation optimization, effectively can reduce the irreversible capacity loss of battery, promote the lithium ion battery negative of the reduction irreversible capacity loss of the energy density of battery.
Present invention also offers a kind of lithium ion battery negative preparation method reducing irreversible capacity loss, processing step is simple, workable, is easy to realize, and scale can apply to the suitability for industrialized production of lithium ion battery completely.
To achieve these goals, the present invention is by the following technical solutions:
A kind of lithium ion battery negative reducing irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, described cathode size is made up of the component of following mass percentage: 25 ~ 45% negative electrode active materials, 0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0 ~ 2% surfactant, 0.0001 ~ 0.01% lithium salts, 50 ~ 70% water, above-mentioned each component percentages sum is 100%.The cathode size formula of anticathode of the present invention is optimized, particularly in cathode size, with the addition of lithium salts, these lithium salts are after cathode size carries out coating baking, one or more layers metastable state SEI membrane structure evenly can be formed at negative pole particle surface, after battery charging and discharging activation, metastable state SEI film becomes more stable through reforming, can avoid lithium ion battery in follow-up discharge and recharge activation process loss part lithium ion to form SEI film, thus reach the irreversible capacity loss effectively reducing battery, promote the object of the energy density of battery.
As preferably, described negative electrode active material is one or more in Delanium, native graphite, composite graphite, soft carbon, hard carbon.
As preferably, described conductive agent is one or more in SP, KS-6, ECP, carbon nano-tube, gas-phase growth of carbon fibre.
As preferably, described binding agent is SBR butadiene-styrene rubber or LA133 aqueous binders.
As preferably, described surfactant is sodium carboxymethylcellulose or polyvinylpyrrolidone.
As preferably, described lithium salts is LiOH, Li 2cO 3, LiF, Li 2c 2o 4, (CH 2oCO 2li) 2, HCOLi, LiCH 2cH 2oCO 2li, CH 3oCO 2one or more in Li.
Reduce a lithium ion battery negative preparation method for irreversible capacity loss, concrete steps are:
(1) lithium salts is dissolved in the water accounting for total Water 10 ~ 20%, obtains lithium salt solution, stand-by.
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl.
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size.
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
Therefore, the present invention has following beneficial effect:
(1) the cathode size formula of anticathode of the present invention is optimized, particularly in cathode size, with the addition of lithium salts, these lithium salts are after cathode size carries out coating baking, one or more layers metastable state SEI membrane structure evenly can be formed at negative pole particle surface, after battery charging and discharging activation, metastable state SEI film becomes more stable through reforming, can avoid lithium ion battery in follow-up discharge and recharge activation process loss part lithium ion to form SEI film, thus reach the irreversible capacity loss effectively reducing battery, promote the object of the energy density of battery;
(2) preparation method of the present invention, processing step is simple, workable, is easy to realize, and scale can apply to the suitability for industrialized production of lithium ion battery completely.
Embodiment
Below by embodiment, the present invention will be further described.
In the present invention, if not refer in particular to, all percentage is unit of weight, and all devices and raw material all can be buied from market or the industry is conventional, and the method in following embodiment, if no special instructions, is this area conventional method.
Embodiment 1
A kind of lithium ion battery negative reducing irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, cathode size is made up of the component of following mass percentage: 25% negative electrode active material, 1% conductive agent, 2% binding agent, 1.9999% surfactant, 0.0001% lithium salts, 70% water, wherein, negative electrode active material is Delanium; Conductive agent is SP; Binding agent is LA133 aqueous binders; Surfactant is sodium carboxymethylcellulose; Lithium salts is LiOH and Li 2cO 3(mass ratio 1:1);
The lithium ion battery negative of this reduction irreversible capacity loss obtains by the following method:
(1) lithium salts is dissolved in the water accounting for total Water 10%, obtains lithium salt solution, stand-by;
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl;
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size;
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
Embodiment 2
A kind of lithium ion battery negative reducing irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, cathode size is made up of the component of following mass percentage: 45% negative electrode active material, 0.3% conductive agent, 2.69% binding agent, 2% surfactant, 0.01% lithium salts, 50% water, wherein, negative electrode active material is Delanium and native graphite (mass ratio 1:1); Conductive agent is KS-6 and gas-phase growth of carbon fibre (mass ratio 3:1); Binding agent is SBR butadiene-styrene rubber; Surfactant is sodium carboxymethylcellulose; Lithium salts is LiOH, Li 2cO 3(CH 2oCO 2li) 2(mass ratio 1:1:1);
The lithium ion battery negative of this reduction irreversible capacity loss obtains by the following method:
(1) lithium salts is dissolved in the water accounting for total Water 15%, obtains lithium salt solution, stand-by;
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl;
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size;
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
Embodiment 3
A kind of lithium ion battery negative reducing irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, cathode size is made up of the component of following mass percentage: 29.995% negative electrode active material, 0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0.005% lithium salts, 60% water, wherein, negative electrode active material is Delanium and soft carbon (mass ratio 1:3); Conductive agent is SP, KS-6 and ECP(mass ratio 1:3:1); Binding agent is LA133 aqueous binders; Lithium salts is HCOLi and LiCH 2cH 2oCO 2li(mass ratio 2:3);
The lithium ion battery negative of this reduction irreversible capacity loss obtains by the following method:
(1) lithium salts is dissolved in the water accounting for total Water 20%, obtains lithium salt solution, stand-by;
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl;
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size;
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
Embodiment 4
A kind of lithium ion battery negative reducing irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, cathode size is made up of the component of following mass percentage: 35% negative electrode active material, 0.3% conductive agent, 0.3% binding agent, 1% surfactant, 0.01% lithium salts, 63.39% water, wherein, negative electrode active material is soft carbon and hard carbon (mass ratio 2:3); Conductive agent is SP, ECP and carbon nano-tube (mass ratio 1:1:1); Binding agent is SBR butadiene-styrene rubber; Surfactant is polyvinylpyrrolidone; Lithium salts is LiF, Li 2c 2o 4, CH 3oCO 2li(mass ratio 1:1:3);
The lithium ion battery negative of this reduction irreversible capacity loss obtains by the following method:
(1) lithium salts is dissolved in the water accounting for total Water 10%, obtains lithium salt solution, stand-by;
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl;
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size;
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
Lithium ion battery negative of the present invention is applied in conventional phosphoric acid lithium iron battery, irreversible capacity loss percentage can be reduced to 3 ~ 5%, compared to Delanium (irreversible capacity loss percentage 10 ~ 15%), the conventional anode such as soft carbon (irreversible capacity loss percentage 10 ~ 20%), effect is very remarkable.
Above-described embodiment is one of the present invention preferably scheme, not does any pro forma restriction to the present invention, also has other variant and remodeling under the prerequisite not exceeding the technical scheme described in claim.

Claims (7)

1. one kind is reduced the lithium ion battery negative of irreversible capacity loss, comprise negative current collector and the cathode size being coated on negative pole currect collecting surface, it is characterized in that, described cathode size is made up of the component of following mass percentage: 25 ~ 45% negative electrode active materials, 0.3 ~ 5% conductive agent, 0.3 ~ 5% binding agent, 0 ~ 2% surfactant, 0.0001 ~ 0.01% lithium salts, 50 ~ 70% water, above-mentioned each component percentages sum is 100%.
2. a kind of lithium ion battery negative reducing irreversible capacity loss according to claim 1, is characterized in that, described negative electrode active material is one or more in Delanium, native graphite, composite graphite, soft carbon, hard carbon.
3. a kind of lithium ion battery negative reducing irreversible capacity loss according to claim 1, is characterized in that, described conductive agent is one or more in SP, KS-6, ECP, carbon nano-tube, gas-phase growth of carbon fibre.
4. a kind of lithium ion battery negative reducing irreversible capacity loss according to claim 1, is characterized in that, described binding agent is SBR butadiene-styrene rubber or LA133 aqueous binders.
5. a kind of lithium ion battery negative reducing irreversible capacity loss according to claim 1, is characterized in that, described surfactant is sodium carboxymethylcellulose or polyvinylpyrrolidone.
6. a kind of lithium ion battery negative reducing irreversible capacity loss according to claim 1, is characterized in that, described lithium salts is LiOH, Li 2cO 3, LiF, Li 2c 2o 4, (CH 2oCO 2li) 2, HCOLi, LiCH 2cH 2oCO 2li, CH 3oCO 2one or more in Li.
7. a lithium ion battery negative preparation method for the reduction irreversible capacity loss as described in any one of claim 1 ~ 6, is characterized in that, concrete steps are:
(1) lithium salts is dissolved in the water accounting for total Water 10 ~ 20%, obtains lithium salt solution, stand-by;
(2) add conductive agent after surfactant and remaining water being mixed to be uniformly dispersed formation conducting resinl;
(3), add negative electrode active material dispersion in conducting resinl after, add binding agent and lithium salt solution, stir final vacuum deaeration, obtains cathode size;
(4) cathode size is evenly coated on negative pole currect collecting surface, dries, obtain lithium ion battery negative.
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Cited By (11)

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CN106684333A (en) * 2017-01-13 2017-05-17 天津中聚新能源科技有限公司 Lithium ion battery anode pulp and preparation method thereof
CN106848218A (en) * 2017-01-13 2017-06-13 浙江大学 A kind of silicon or silicon alloy composite lithium ion battery cathode material containing biethyl diacid lithium borate and its preparation method and application
CN107394208A (en) * 2017-06-30 2017-11-24 中天储能科技有限公司 A kind of preparation method of the lithium battery pole slice of water-based binder and application water-based binder
CN107732154A (en) * 2017-11-10 2018-02-23 江苏华富储能新技术股份有限公司 Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge
CN107910520A (en) * 2017-11-10 2018-04-13 江苏华富储能新技术股份有限公司 A kind of lithium ion battery cathode slurry, negative material and preparation method thereof
CN108199004A (en) * 2017-12-25 2018-06-22 深圳市山木新能源科技股份有限公司 The manufacturing method and electrode slice of electrode slice
CN110190245A (en) * 2019-06-17 2019-08-30 珠海格力电器股份有限公司 Negative electrode slurry containing stable lithium salt, preparation method, negative electrode plate and lithium ion battery
CN110492103A (en) * 2019-08-19 2019-11-22 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of lithium ion battery silicon-carbon cathode binder and products thereof and application
WO2020175362A1 (en) * 2019-02-28 2020-09-03 パナソニック株式会社 Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell
CN112768642A (en) * 2019-11-01 2021-05-07 广州汽车集团股份有限公司 Negative electrode material and preparation method thereof, negative electrode plate, lithium ion battery cell and lithium ion battery pack and application thereof
CN114094110A (en) * 2022-01-24 2022-02-25 河南电池研究院有限公司 Graphite negative electrode for solid lithium ion battery

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CN106684333A (en) * 2017-01-13 2017-05-17 天津中聚新能源科技有限公司 Lithium ion battery anode pulp and preparation method thereof
CN106848218A (en) * 2017-01-13 2017-06-13 浙江大学 A kind of silicon or silicon alloy composite lithium ion battery cathode material containing biethyl diacid lithium borate and its preparation method and application
CN106684333B (en) * 2017-01-13 2019-12-13 天津中聚新能源科技有限公司 Lithium ion battery cathode slurry and preparation method thereof
CN107394208A (en) * 2017-06-30 2017-11-24 中天储能科技有限公司 A kind of preparation method of the lithium battery pole slice of water-based binder and application water-based binder
CN107910520A (en) * 2017-11-10 2018-04-13 江苏华富储能新技术股份有限公司 A kind of lithium ion battery cathode slurry, negative material and preparation method thereof
CN107732154A (en) * 2017-11-10 2018-02-23 江苏华富储能新技术股份有限公司 Small lithium ion battery of loss of capacitance and preparation method thereof after a kind of circulation electric discharge
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WO2020175362A1 (en) * 2019-02-28 2020-09-03 パナソニック株式会社 Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell
CN113491022A (en) * 2019-02-28 2021-10-08 松下电器产业株式会社 Slurry for nonaqueous electrolyte secondary battery electrode, method for producing slurry for nonaqueous electrolyte secondary battery electrode, electrode for nonaqueous electrolyte secondary battery, and nonaqueous electrolyte secondary battery
JPWO2020175362A1 (en) * 2019-02-28 2021-12-23 パナソニック株式会社 Non-aqueous electrolyte secondary battery electrode slurry, non-aqueous electrolyte secondary battery electrode slurry manufacturing method, non-aqueous electrolyte secondary battery electrode and non-aqueous electrolyte secondary battery
US20220149377A1 (en) * 2019-02-28 2022-05-12 Panasonic Corporation Slurry for non-aqueous electrolyte secondary cell, method for manufacturing slurry for non-aqueous electrolyte secondary cell, electrode for non-aqueous electrolyte secondary cell, and non-aqueous electrolyte secondary cell
JP7480114B2 (en) 2019-02-28 2024-05-09 パナソニックホールディングス株式会社 Method for producing slurry for non-aqueous electrolyte secondary battery electrodes
CN110190245A (en) * 2019-06-17 2019-08-30 珠海格力电器股份有限公司 Negative electrode slurry containing stable lithium salt, preparation method, negative electrode plate and lithium ion battery
CN110492103A (en) * 2019-08-19 2019-11-22 上海纳米技术及应用国家工程研究中心有限公司 A kind of preparation method of lithium ion battery silicon-carbon cathode binder and products thereof and application
CN112768642A (en) * 2019-11-01 2021-05-07 广州汽车集团股份有限公司 Negative electrode material and preparation method thereof, negative electrode plate, lithium ion battery cell and lithium ion battery pack and application thereof
CN114094110A (en) * 2022-01-24 2022-02-25 河南电池研究院有限公司 Graphite negative electrode for solid lithium ion battery
CN114094110B (en) * 2022-01-24 2022-04-22 河南电池研究院有限公司 Graphite cathode for solid lithium ion battery

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