CN106299249B - A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry - Google Patents

A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry Download PDF

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Publication number
CN106299249B
CN106299249B CN201610696612.8A CN201610696612A CN106299249B CN 106299249 B CN106299249 B CN 106299249B CN 201610696612 A CN201610696612 A CN 201610696612A CN 106299249 B CN106299249 B CN 106299249B
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slurry
ternary material
glue
nickelic ternary
modified
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CN106299249A (en
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贺雨雨
冯德圣
陈炜
张宏立
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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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
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/1399—Processes of manufacture of electrodes based on electro-active polymers
    • 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

A method of inhibit nickelic ternary material to close slurry gel and improve Stability of Slurry, is related to field of lithium ion battery.The purpose is to provide a kind of method that can effectively avoid the problem that occurring gel during nickelic ternary material conjunction slurry and improving Stability of Slurry.It is characterized in that by using modified PVDF and changes slurry-stirring process, PVDF is inhibited to generate double bond structure, so that the certainly nickelic ternary material of resolution closes the difficult problem of slurry and improves the stability of slurry.This method can be substantially reduced nickelic ternary material and close requirement of the slurry to ambient humidity, improve and close slurry success rate, while this method also contributes to the stability of slurry.The present invention has great importance for the industrial application development of nickelic ternary material.

Description

A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry
Technical field
The present invention relates to technical field of lithium ion, it is related to a kind of inhibiting nickelic ternary material to close slurry gel and improve to starch Expect the method for stability.
Background technique
Since new-energy automobile is classified as one of the main contents of pilot special project by 13 planning, while requiring single battery Energy density >=300KWh/g, exploitation high security, the long-life, lithium ion battery with high energy density become dynamic lithium battery hair The main target of exhibition, wherein the core for improving battery energy density is exactly to improve the gram volume performance of positive electrode.For at present, Nickelic ternary material is higher since gram volume plays (NCA gram volume plays reachable 200mAh/g), is the following dynamic lithium battery The developing direction of positive ternary material.But the residual alkali amount increase of material surface causes to close the slurry easy water absorbed in environment in the process Point, gelatin phenomenon is formed, causes to close slurry failure.Therefore the processability of nickelic ternary material is the bottleneck that industrialization promotes.
Patent CN105336918A discloses a kind of preparation method of nickelic system's positive electrode of lithium ion battery, using in glue The mode of acetone and one to two kinds of additives is added in liquid, effectively eliminates gelatin phenomenon.And in fact, repeatedly charging process not It only will affect the consistency of slurry, it is often more important that, influence of the use of additive to battery is unknown.Meanwhile mixing is molten Agent can also influence the dry quality and efficiency of later period coating to a certain extent.
Summary of the invention
The technical problem to be solved by the present invention is to the nickelic ternary materials of lithium ion battery to close slurry gel problem.
A method of inhibit nickelic ternary material to close slurry gel and improve Stability of Slurry, it is characterised in that: is preparing During closing slurry, binder is used as using modified Kynoar (PVDF), and be added and be modified step by step during closing slurry Kynoar glue.
Preferably, the molecular formula of the Kynoar of the modification are as follows:
Wherein, X is hydrophilic radical.
Further scheme, the hydrophilic radical are-SO3H ,-COOH or-NH2。
Preferably, the nickelic ternary material is LiNixCoyM1-x-yO2, wherein X >=0.6；M is Mn or Al.
Preferably, the process that slurry is closed in the preparation includes the following steps:
(1) prepared by modified polyvinilidene fluoride glue；
(2) conductive agent is added in the modified polyvinilidene fluoride glue for the part that step (1) prepares, is stirred；
(3) nickelic ternary material is added in the slurry of step (2), is stirred；
(4) remaining modified polyvinilidene fluoride glue is added in the slurry of step (3), high-speed stirred.
Further, the quality of the modified polyvinilidene fluoride glue of part is glue gross mass in the step (2) 10-40%.
Further, used when the preparation of step (1) the modified polyvinilidene fluoride glue N-Methyl pyrrolidone as Close slurry solvent.
Further, the quality of modified polyvinilidene fluoride accounts for modified polyvinilidene fluoride glue always admittedly in the step (1) The 1-5% of weight, the solid content of modified polyvinilidene fluoride glue are 5-10%.
The beneficial effects of the present invention are:
The slurry-stirring process of glue is added by using modified PVDF and substep, eliminates nickelic ternary material and closes slurry gel The phenomenon that, while Stability of Slurry can be significantly improved.Modified PVDF and change slurry-stirring process not only can effectively eliminate The de- HF of PVDF reacts, and inhibits the bridging reaction between the polymer chain of binder, eliminates nickelic ternary material and closes slurry gel Phenomenon, while Stability of Slurry can be significantly improved.
Detailed description of the invention
Fig. 1 is slurry-stirring process flow chart of the present invention.
Fig. 2 is embodiment 1 and 3 slurry viscosity of comparative example and time chart.
Specific embodiment
Below with reference to table and embodiment, the present invention is described in detail.
Embodiment 1
The present embodiment just extremely LiNixCoyMn1-x-yO2(x >=0.6), it is modifiedMass fraction It is 2.5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 80%RH.Using conjunction Steps are as follows for slurry: (1) modified PVDF glue preparation, solid content 8%；(2) Sp and Ks-6 is added to 10% modification PVDF glue In, stirring；(3) positive active material is added in (2) slurry, is stirred；(4) remaining modified PVDF glue is added to (3) in slurry, stirring；(5) high-speed stirred；(6) viscosity is adjusted；(7) it discharges.Slurry fluidity is good, does not occur gelatin phenomenon, slurry Material discharging viscosity is 4521mPaS.Painting effect is good, and with the extension of standing time, slurry viscosity variation is little, such as Fig. 2.
Comparative example 1
This comparative example just extremely LiNixCoyMn1-x-yO2(x >=0.6), it is unmodifiedQuality Score is 2.5%, and conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 55%RH.It adopts With slurry is closed, steps are as follows: (1) preparation of PVDF glue, solid content 8%；(2) Sp and Ks-6 are added in whole PVDF glues, Stirring；(3) positive active material is added in (2) in slurry, is stirred；(4) high-speed stirred；(5) viscosity is adjusted；(6) it discharges.Slurry There is serious gelatin phenomenon in material.
Comparative example 2
This comparative example just extremely LiNixCoyMn1-x-yO2(x >=0.6),Mass fraction is 2.5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 50%RH.It is starched using closing Steps are as follows: (1) prepared by PVDF glue, solid content 8%；(2) Sp and Ks-6 are added in 10%PVDF glue, are stirred；(3) will Positive active material is added in (2) slurry, stirring；(4) remaining PVDF glue is added in (3) slurry, is stirred；(5) high Speed stirring；(6) viscosity is adjusted；(7) it discharges.When discharging, slurry does not occur gelatin phenomenon, but after shelving 2h under room temperature, pulp gel.
Comparative example 3
This comparison just extremely LiNixCoyMn1-x-yO2(x >=0.6), it is modifiedMass fraction It is 2.5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 55%RH.Using conjunction Steps are as follows for slurry: (1) preparation of modified PVDF glue, solid content 8%；(2) Sp and Ks-6 is added to all modified PVDF glue In liquid, stirring；(3) positive active material is added in (2) in slurry, is stirred；(4) high-speed stirred；(5) viscosity is adjusted；(6) go out Material.When discharging, slurry fluidity is good, gelatin phenomenon does not occur.Stock discharge viscosity is 4287mPaS,
Coating is good, but with the extension of standing time, slurry viscosity quickly increases, until there is gel, such as Fig. 2.It is real Apply example 2
The present embodiment just extremely LiNixCoyMn1-x-yO2(x >=0.6), it is modifiedMass fraction It is 1%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 80%RH.Using conjunction Steps are as follows for slurry: (1) preparation of modified PVDF glue, solid content 5%；(2) Sp and Ks-6 is added to 20% modification PVDF In glue, stirring；(3) positive active material is added in (2) in slurry, is stirred；(4) remaining modified PVDF glue is added Enter into (3) slurry, stirs；(5) high-speed stirred；(6) viscosity is adjusted；(7) it discharges.Slurry fluidity is good, gel does not occur Phenomenon, coating are good.Stock discharge viscosity is 4928mPaS, and after placing 6 days, slurry viscosity variation is 5461mPa less S。
Embodiment 3
The present embodiment just extremely LiNixCoyAl1-x-yO2(x >=0.6), it is modifiedMass fraction It is 5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), humidity level 80%RH.Using conjunction Steps are as follows for slurry: (1) preparation of modified PVDF glue, solid content 10%；(2) Sp and Ks-6 is added to 40% modification PVDF In glue, stirring；(3) positive active material is added in (2) in slurry, is stirred；(4) the modified PVDF glue of residue is added Into (3) slurry, stirring；(5) high-speed stirred；(6) viscosity is adjusted；(7) it discharges.Slurry fluidity is good, and it is existing gel do not occur As coating is good.Stock discharge viscosity is 5162mPaS, and after placing 6 days, slurry viscosity variation is 5748mPaS less.
By the above embodiments and comparative example as it can be seen that using modified PVDF and changing slurry-stirring process, can not only disappear Except nickelic anode closes slurry gel problem, the stability of slurry can also be improved.
Above content is only citing made for the present invention and explanation, affiliated those skilled in the art are to being retouched The specific embodiment stated does various modifications or additions or is substituted in a similar manner, as long as it does not deviate from the concept of invention Or beyond the scope defined by this claim, it is within the scope of protection of the invention.

Claims (6)

1. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry, it is characterised in that: closed in preparation During slurry, using modified Kynoar as binder, first prepare modified Kynoar glue, by conductive agent plus Enter into partially modified glue, stirs, then nickelic ternary material is added in slurry and is stirred, the glue for being finally again modified residue Liquid is added, and obtains slurry；The molecular formula of the Kynoar of the modification are as follows:
Wherein, X is hydrophilic radical-SO3H ,-COOH or-NH2。
2. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry as described in claim 1, Be characterized in that: the nickelic ternary material is LiNixCoyM1-x-yO2, wherein x>=0.6,0<y<0.4；M is Mn or Al.
3. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry as described in claim 1, It is characterized in that, the process that slurry is closed in the preparation includes the following steps:
(1) prepared by modified polyvinilidene fluoride glue；
(2) conductive agent is added in the partially modified Kynoar glue that step (1) prepares, is stirred；
(3) nickelic ternary material is added in the slurry of step (2), is stirred；
(4) remaining modified polyvinilidene fluoride glue is added in the slurry of step (3), high-speed stirred.
4. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry as claimed in claim 3, Be characterized in that: the quality of part modified polyvinilidene fluoride glue is the 10-40% of glue gross mass in the step (2).
5. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry as claimed in claim 3, Be characterized in that: step (1) the modified polyvinilidene fluoride glue uses N-Methyl pyrrolidone as conjunction slurry solvent when preparing.
6. a kind of method for inhibiting nickelic ternary material to close slurry gel and improve Stability of Slurry as claimed in claim 3, Be characterized in that: the quality of modified polyvinilidene fluoride accounts for the 1- of modified polyvinilidene fluoride glue total solid quality in the step (1) 5%, the solid content of modified polyvinilidene fluoride glue is 5-10%.
CN201610696612.8A 2016-08-21 2016-08-21 A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry Active CN106299249B (en)

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CN108336355B (en) * 2017-01-17 2020-09-15 中航锂电（洛阳）有限公司 Lithium ion battery anode slurry and preparation method thereof
CN113488652A (en) * 2021-06-30 2021-10-08 昆山兴能能源科技有限公司 Method for improving agglomeration of lithium ion ternary positive electrode slurry

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CN104577013A (en) * 2015-01-10 2015-04-29 鸿德新能源科技有限公司 Water-based ceramic diaphragm slurry and application thereof in lithium ion battery
CN105470461A (en) * 2014-10-15 2016-04-06 万向A一二三***有限公司 High-nickel base cathode paste for lithium-ion battery and preparation method of high-nickel base cathode paste

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WO2014046078A1 (en) * 2012-09-18 2014-03-27 株式会社クレハ Binder for nonaqueous electrolyte secondary cell, binder solution for nonaqueous electrolyte secondary cell, anode mixture for nonaqueous electrolyte secondary cell, and uses thereof

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Publication number Priority date Publication date Assignee Title
CN1780034A (en) * 2004-11-22 2006-05-31 中国电子科技集团公司第十八研究所 Production of uniform sizing material for lithium ion cell electrode
CN101212045A (en) * 2006-12-30 2008-07-02 比亚迪股份有限公司 Method for proportioning anode paste of Li-ion secondary battery
CN101694872A (en) * 2009-10-21 2010-04-14 保定风帆新能源有限公司 Mixing preparation method of pulp of lithium ion battery
CN105470461A (en) * 2014-10-15 2016-04-06 万向A一二三***有限公司 High-nickel base cathode paste for lithium-ion battery and preparation method of high-nickel base cathode paste
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Application publication date: 20170104

Assignee: NANJING GUOXUAN BATTERY CO., LTD.

Assignor: Hefei Guoxuan High-Tech Power Energy Co., Ltd.

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Denomination of invention: A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry

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