CN106299249A - A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry - Google Patents

A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry Download PDF

Info

Publication number
CN106299249A
CN106299249A CN201610696612.8A CN201610696612A CN106299249A CN 106299249 A CN106299249 A CN 106299249A CN 201610696612 A CN201610696612 A CN 201610696612A CN 106299249 A CN106299249 A CN 106299249A
Authority
CN
China
Prior art keywords
slurry
ternary material
nickelic ternary
close
glue
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.)
Granted
Application number
CN201610696612.8A
Other languages
Chinese (zh)
Other versions
CN106299249B (en
Inventor
贺雨雨
冯德圣
陈炜
张宏立
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Hefei Gotion High Tech Power Energy Co Ltd
Original Assignee
Hefei Guoxuan High Tech Power Energy Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Hefei Guoxuan High Tech Power Energy Co Ltd filed Critical Hefei Guoxuan High Tech Power Energy Co Ltd
Priority to CN201610696612.8A priority Critical patent/CN106299249B/en
Publication of CN106299249A publication Critical patent/CN106299249A/en
Application granted granted Critical
Publication of CN106299249B publication Critical patent/CN106299249B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/139—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 kind of method suppressing the conjunction of nickelic ternary material to starch gel and raising Stability of Slurry, relates to field of lithium ion battery.Its objective is that providing a kind of can be prevented effectively from the problem occurring gel during nickelic ternary material closes slurry and the method improving Stability of Slurry.It is characterized in that, by using modified PVDF and changing slurry-stirring process, suppression PVDF generates double bond structure, thus clears up the most nickelic ternary material and close the problem of slurry difficulty and improve the stability of slurry.The method can substantially reduce nickelic ternary material and close the slurry requirement to ambient humidity, improves and closes slurry success rate, and the method also contributes to the stability of slurry simultaneously.The present invention has great importance for the commercial application development of nickelic ternary material.

Description

A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry
Technical field
The present invention relates to technical field of lithium ion, relate to a kind of suppression nickelic ternary material conjunction slurry gel and starch with improving The method of material stability.
Background technology
Since new-energy automobile is classified as one of special main contents of pilot by 13 planning, require cell simultaneously Energy density >=300KWh/g, exploitation high security, long-life, lithium ion battery with high energy density become dynamic lithium battery and send out The main target of exhibition, the core wherein improving battery energy density is exactly that the gram volume improving positive electrode plays.For Mu Qian, Nickelic ternary material higher owing to gram volume plays (NCA gram volume plays can arrive 200mAh/g), is following dynamic lithium battery The developing direction of positive pole ternary material.But the residual alkali number increase of material surface easily absorbs the water in environment during causing closing slurry Point, form gelatin phenomenon, cause closing and starch unsuccessfully.The processability of the most nickelic ternary material is the bottleneck that industrialization advances.
Patent CN105336918A discloses the preparation method of a kind of lithium ion battery nickelic system positive electrode, uses at glue Liquid adds acetone and the mode of one to two kinds of additives, effectively eliminates gelatin phenomenon.And it is true that repeatedly charging process is not Only can affect the concordance of slurry, it is often more important that, using of additive is unknown on the impact of battery.Meanwhile, mix molten Agent also can affect quality and the efficiency that later stage coating is dried to a certain extent.
Summary of the invention
The technical problem to be solved in the present invention is that the nickelic ternary material of lithium ion battery closes slurry gel problem.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry, it is characterised in that: in preparation During closing slurry, the Kynoar (PVDF) of employing modification is as binding agent, and substep addition is modified during closing slurry Kynoar glue.
Preferably, the molecular formula of the Kynoar of described modification is:
Wherein, X is hydrophilic radical.
Further scheme, described hydrophilic radical is-SO3H ,-COOH or-NH2。
Preferably, described nickelic ternary material is LiNixCoyM1-x-yO2, wherein, X >=0.6；M is Mn or Al.
Preferably, the process that slurry is closed in described preparation comprises the steps:
(1) prepared by modified polyvinilidene fluoride glue；
(2) conductive agent is joined in the modified polyvinilidene fluoride glue of the part that step (1) prepares, stirring；
(3) nickelic ternary material is joined in the slurry of step (2), stirring；
(4) remaining modified polyvinilidene fluoride glue is joined in the slurry of step (3), high-speed stirred.
Further, in described step (2), the quality of the modified polyvinilidene fluoride glue of part is glue gross mass 10-40%.
Further, step (1) described modified polyvinilidene fluoride glue uses N-Methyl pyrrolidone conduct when preparing Close slurry solvent.
Further, in described step (1), the quality of modified polyvinilidene fluoride always accounts for modified polyvinilidene fluoride glue admittedly The 1-5% of weight, the solid content of modified polyvinilidene fluoride glue is 5-10%.
The beneficial effects of the present invention is:
By using modified PVDF and substep to add the slurry-stirring process of glue, eliminate nickelic ternary material and close slurry gel Phenomenon, simultaneously can significantly improve Stability of Slurry.Modified PVDF and change slurry-stirring process are possible not only to effectively eliminate The de-HF reaction of PVDF, the bridge formation reaction between the polymer chain of suppression binding agent, eliminate nickelic ternary material and close slurry gel Phenomenon, can significantly improve Stability of Slurry simultaneously.
Accompanying drawing explanation
Fig. 1 is slurry-stirring process flow chart of the present invention.
Fig. 2 is embodiment 1 and comparative example 3 slurry viscosity and time chart.
Specific embodiments
Below in conjunction with table and embodiment, the present invention is described in detail.
Embodiment 1
The present embodiment the most extremely LiNixCoyMn1-x-yO2(x >=0.6), modifiedMass fraction Being 2.5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), and humidity level is 80%RH.Use and close Slurry step is as follows: prepared by (1) modified PVDF glue, solid content 8%；(2) Sp Yu Ks-6 joins the modified PVDF glue of 10% In, stirring；(3) positive active material is joined in (2) slurry, stirring；(4) remaining modified PVDF glue is joined (3) in slurry, stirring；(5) high-speed stirred；(6) viscosity is adjusted；(7) discharging.Slurry fluidity is good, gelatin phenomenon does not occurs, slurry Material discharging viscosity is 4521mPa S.Painting effect is good, and along with the prolongation of standing time, slurry viscosity change is little, as Fig. 2.
Comparative example 1
This comparative example the most extremely LiNixCoyMn1-x-yO2(x >=0.6), unmodifiedQuality Mark is 2.5%, and conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), and humidity level is 55%RH.Adopt With closing, slurry step is as follows: the preparation of (1) PVDF glue, solid content is 8%；(2) during Sp Yu Ks-6 joins whole PVDF glue, Stirring；(3) positive active material is joined in (2) in slurry, stirring；(4) high-speed stirred；(5) viscosity is adjusted；(6) discharging.Slurry There is serious gelatin phenomenon in material.
Comparative example 2
This comparative example the most 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%), and humidity level is 50%RH.Use and close slurry Step is as follows: prepared by (1) PVDF glue, solid content 8%；(2) during Sp Yu Ks-6 joins 10%PVDF glue, stirring；(3) will Positive active material joins in (2) slurry, stirring；(4) residue PVDF glue is joined in (3) slurry, stirring；(5) high Speed stirring；(6) viscosity is adjusted；(7) discharging.During discharging, there is not gelatin phenomenon in slurry, but after shelving 2h under room temperature, pulp gel.
Comparative example 3
This contrast the most extremely LiNixCoyMn1-x-yO2(x >=0.6), modifiedMass fraction Being 2.5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), and humidity level is 55%RH.Use and close Slurry step is as follows: the preparation of (1) modified PVDF glue, solid content is 8%；(2) Sp Yu Ks-6 joins the most modified PVDF glue In liquid, stirring；(3) positive active material is joined in (2) in slurry, stirring；(4) high-speed stirred；(5) viscosity is adjusted；(6) go out Material.During discharging, slurry fluidity is good, gelatin phenomenon does not occur.Stock discharge viscosity is 4287mPa S,
Coating is good, but along with the prolongation of standing time, slurry viscosity quickly increases, until there is gel, such as Fig. 2.Real Execute example 2
The present embodiment the most extremely LiNixCoyMn1-x-yO2(x >=0.6), modifiedMass fraction Being 1%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), and humidity level is 80%RH.Use and close Slurry step is as follows: the preparation of (1) modified PVDF glue, solid content is 5%；(2) Sp Yu Ks-6 joins the modified PVDF of 20% In glue, stirring；(3) positive active material is joined in (2) in slurry, stirring；(4) remaining modified PVDF glue is added Enter in (3) slurry, stirring；(5) high-speed stirred；(6) viscosity is adjusted；(7) discharging.Slurry fluidity is good, gel does not occur Phenomenon, coating is good.Stock discharge viscosity is 4928mPa S, and after placing 6 days, slurry viscosity change is little, for 5461mPa S。
Embodiment 3
The present embodiment the most extremely LiNixCoyAl1-x-yO2(x >=0.6), modifiedMass fraction Being 5%, conductive agent is Sp (mass fraction 2%) and Ks-6 (mass fraction 1%), and humidity level is 80%RH.Use and close Slurry step is as follows: the preparation of (1) modified PVDF glue, solid content is 10%；(2) Sp Yu Ks-6 joins the modified PVDF of 40% In glue, stirring；(3) positive active material is joined in (2) in slurry, stirring；(4) modified for residue PVDF glue is added In (3) slurry, stirring；(5) high-speed stirred；(6) viscosity is adjusted；(7) discharging.Slurry fluidity is good, does not occur that gel is existing As, coating is good.Stock discharge viscosity is 5162mPa S, and after placing 6 days, slurry viscosity change is little, for 5748mPa S.
From the above embodiments and comparative example, use modified PVDF and change slurry-stirring process, being possible not only to disappear Except nickelic positive pole closes slurry gel problem, it is also possible to improve the stability of slurry.
Above content is only citing made for the present invention and explanation, and affiliated those skilled in the art are to being retouched The specific embodiment stated makes various amendment or supplements or use similar mode to substitute, without departing from the design of invention Or surmount scope defined in the claims, protection scope of the present invention all should be belonged to.

Claims (8)

1. one kind is suppressed nickelic ternary material to close slurry gel and the method improving Stability of Slurry, it is characterised in that: close in preparation During slurry, the Kynoar of employing modification is as binding agent, and the poly-inclined fluorine of substep addition modification during closing slurry Ethylene glue.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 1, its Being characterised by, the molecular formula of the Kynoar of described modification is:
Wherein, X is hydrophilic radical.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 2, its It is characterised by: described hydrophilic radical is-SO3H ,-COOH or-NH2。
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 1, its It is characterised by: described nickelic ternary material is LiNixCoyM1-x-yO2, wherein, X >=0.6；M is Mn or Al.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 1, its Being characterised by, the process that slurry is closed in described preparation comprises the steps:
(1) prepared by modified polyvinilidene fluoride glue；
(2) conductive agent is joined in the partially modified Kynoar glue that step (1) prepares, stirring；
(3) nickelic ternary material is joined in the slurry of step (2), stirring；
(4) residue modified polyvinilidene fluoride glue is joined in the slurry of step (3), high-speed stirred.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 5, its It is characterised by: the 10-40% that quality is glue gross mass of part modified polyvinilidene fluoride glue in described step (2).
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 5, its It is characterised by: time prepared by step (1) described modified polyvinilidene fluoride glue, use N-Methyl pyrrolidone as closing slurry solvent.
A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry the most as claimed in claim 5, its It is characterised by: in described step (1), the quality of modified polyvinilidene fluoride accounts for the 1-of modified polyvinilidene fluoride glue total solid quality 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610696612.8A CN106299249B (en) 2016-08-21 2016-08-21 A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610696612.8A CN106299249B (en) 2016-08-21 2016-08-21 A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry

Publications (2)

Publication Number Publication Date
CN106299249A true CN106299249A (en) 2017-01-04
CN106299249B CN106299249B (en) 2019-11-01

Family

ID=57661969

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610696612.8A Active CN106299249B (en) 2016-08-21 2016-08-21 A method of inhibit nickelic ternary material to close slurry gel and improves Stability of Slurry

Country Status (1)

Country Link
CN (1) CN106299249B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108336355A (en) * 2017-01-17 2018-07-27 中航锂电（洛阳）有限公司 A kind of lithium ion battery anode glue size 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

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014077A1 (en) * 2004-07-15 2006-01-19 Matsushita Electric Industrial Co., Ltd. Process of preparing coating for positive electrode materials for lithium secondary batteries and positive electrodes for lithium secondary batteries
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
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
CN104584288A (en) * 2012-09-18 2015-04-29 株式会社吴羽 Binder for nonaqueous electrolyte secondary cell, binder solution for nonaqueous electrolyte secondary cell, anode mixture for nonaqueous electrolyte secondary cell, and uses thereof
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

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060014077A1 (en) * 2004-07-15 2006-01-19 Matsushita Electric Industrial Co., Ltd. Process of preparing coating for positive electrode materials for lithium secondary batteries and positive electrodes for lithium secondary batteries
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
CN104584288A (en) * 2012-09-18 2015-04-29 株式会社吴羽 Binder for nonaqueous electrolyte secondary cell, binder solution for nonaqueous electrolyte secondary cell, anode mixture for nonaqueous electrolyte secondary cell, and uses thereof
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
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

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108336355A (en) * 2017-01-17 2018-07-27 中航锂电（洛阳）有限公司 A kind of lithium ion battery anode glue size and preparation method thereof
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

Also Published As

Publication number Publication date
CN106299249B (en) 2019-11-01

Similar Documents

Publication Publication Date Title
CN105914377B (en) A kind of pluralistic function modified high-molecular lithium ion battery binder and the application in electrochemical energy storing device
CN102585111B (en) Modified epoxy emulsion and preparation method thereof
KR101597745B1 (en) Binder for Secondary Battery and Secondary Battery Comprising the Same
JP4356294B2 (en) Electrode binder composition, electrode slurry, electrode, and battery
CN106281147A (en) A kind of water base binders for electrodes and preparation method
CN105367696A (en) Elastic raindrop impression resisting styrene-acrylic emulsion and preparation method thereof
CN105047845A (en) High-dielectric constant nano-composite coating diaphragm and preparation method thereof
CN1765025A (en) Composite binder for an electrode with dispersants chemically bound
JP7064881B2 (en) Water-based binder composition for secondary battery electrodes, slurry for secondary battery electrodes, binders, secondary battery electrodes, and secondary batteries
WO2006069500A1 (en) Manufacture method for positive electrode sheet of lithium-ion battery and positive electrode sheet and lithium-ion battery using the same
JP2012104406A (en) Binder for electrode
CN106797032A (en) Adhesive composition for secondary cell and the electrode comprising it and lithium secondary battery
JP5970183B2 (en) Electrode binder
JP2012234703A (en) Metal salt-containing binder
JP2016058185A (en) Binder composition for power storage device electrode, slurry for power storage device electrode, power storage device electrode, and power storage device
CN106299249A (en) A kind of method suppressing nickelic ternary material to close slurry gel and raising Stability of Slurry
JP2014175106A (en) Binder of lithium ion secondary battery electrode, slurry for electrodes, lithium ion secondary battery electrode, and lithium ion secondary battery
WO2015093765A1 (en) Method for preparing aqueous binder for positive electrode active material of secondary battery
CN104530304A (en) Low-Tg acrylate emulsion for cement-based building materials, and preparation method thereof
JP4438102B2 (en) Binder for battery, slurry for battery electrode, electrode for lithium secondary battery, and lithium secondary battery
CN107641170A (en) Polymer emulsion, preparation method and the aqueous binder of preparation, method and application
CN111699579B (en) Slurry for nonaqueous battery electrode, and method for producing nonaqueous battery
JP2016058184A (en) Binder composition for power storage device electrode, slurry for power storage device electrode, power storage device electrode, and power storage device
CN108666578B (en) Lithium ion battery cathode water system binder composition and preparation process thereof
CN106384816A (en) High-nickel ternary lithium ion battery positive electrode slurry and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20170104

Assignee: NANJING GUOXUAN BATTERY CO., LTD.

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

Contract record no.: 2017320000046

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

License type: Exclusive License

Record date: 20170306

EE01 Entry into force of recordation of patent licensing contract
GR01 Patent grant
GR01 Patent grant