CN105470462A - Preparation method of negative electrode for lithium-ion battery - Google Patents
Preparation method of negative electrode for lithium-ion battery Download PDFInfo
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- CN105470462A CN105470462A CN201510137268.4A CN201510137268A CN105470462A CN 105470462 A CN105470462 A CN 105470462A CN 201510137268 A CN201510137268 A CN 201510137268A CN 105470462 A CN105470462 A CN 105470462A
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- ion battery
- negative electrode
- lithium ion
- lithium
- negative
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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
- 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 relates to the technical field of lithium-ion batteries, and aims at solving the problem that an existing lithium-ion battery has irreversible capacity loss. The invention provides a preparation method of a negative electrode for a lithium-ion battery. A lithium salt is added to homogenate slurry of the negative electrode; and a metastable SEI film is formed on the surface of the negative electrode. The metastable SEI film is firstly formed on the surface of the negative electrode; and the SEI film is formed without consuming lithium ions at a cathode in the subsequent charge-discharge process, so that the irreversible capacity loss is reduced.
Description
Technical field
The present invention relates to technical field of lithium ion, relate in particular to a kind of preparation method of negative electrode for lithium ion battery.
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 looked at as a kind of build-in attribute of lithium ion battery, by forming SEI film, although the insertion of solvent molecule in electrolyte in cyclic process can be prevented, be conducive to the structure of stable negative terminal surface, but the also loss portion capacity of battery, first charge-discharge irreversible capacity is increased, thus has badly influenced giving full play to of the energy content of battery.Shown by large quantity research, 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.
Publication number is that the Chinese patent of 102916165A discloses a kind of method of mending lithium to anode plate for lithium ionic cell, which disclose in an inert atmosphere, by organolithium spray solution or drip in negative plate surface, make the lithium ion in organolithium solution be reduced into lithium metal and embed in negative plate, then dry negative plate.Although this invention is passed through even organolithium spray solution or is dripped on the surface of negative plate, achieve " wet method benefit lithium ", thus metallic lithium powder is aerial floating when effectively avoiding dry method benefit lithium, ensure production safety, and the amount of mending lithium accurately can be controlled by the time of the amount of the organolithium solution that sprays or drip, sprinkling or dropping, to reach the object of evenly mending lithium, what prevent negative plate analyses lithium and distortion, improve the efficiency first of battery, and then improve the energy density of battery.But because the whole technical process of this method all will be carried out in an inert atmosphere, cause complex procedures, harsh to environmental requirement, increase the cost of manufacture of cathode pole piece.And the formation of the SEI film of its negative terminal surface is still by after later stage cell activation, and the dissolving of lithium metal is reached.
Summary of the invention
The problem of irreversible capacity loss is there is for solving current lithium ion battery, the present invention proposes a kind of negative electrode for lithium ion battery preparation method, the present invention in charge and discharge process without the need to consuming the lithium ion of negative electrode to form SEI film, thus reduce irreversible capacity loss.
The present invention is achieved by the following technical solutions: described in a kind of preparation method of negative electrode for lithium ion battery, negative pole preparation method for add lithium salts in negative pole homogenate slurry, then negative pole homogenate slurry is adopted the mode of spraying or roller coat in conductive foil, namely coating obtains the lithium ion battery negative that surface is rich in metastable state SEI film after drying.The present invention by first forming the metastable SEI film of one deck in negative terminal surface, like this in follow-up charge and discharge process without the need to consuming the lithium ion of negative electrode to form SEI film, thus reduction irreversible capacity loss.
Described preparation method is following steps:
(1) surfactant is water-soluble, make glue,
Adding surfactant impels negative terminal surface to form one or more layers metastable state SEI membrane structure, and after carrying out coating baking, metastable state SEI film will be evenly distributed in negative pole particle surface.
(2) in glue, add conductive agent and make conducting resinl,
(3) mix after adding graphite in conducting resinl, then add binding agent, lithium salts, add water after mixing and regulate viscosity and solid content, obtain homogenate slurry,
As preferably, lithium salts is first dissolved in water, adds after making lithium salt solution again.As preferably, solid content is 30 ~ 50%, and the viscosity of homogenate slurry is 2000 ~ 5000cps.
(4) adopt the mode of spraying or roller coat after being sieved by homogenate slurry in conductive foil, namely coating obtains the lithium ion battery negative that surface is rich in metastable state SEI film after drying.
As preferably, conductive foil selects conventional copper foil,
As preferably, after sieving, fineness is less than 40um.
As preferably, when conducting electricity foil coating, adopting the mode of spraying or roller coat by homogenate slurry coating on negative conductive foil, after oven dry, namely obtaining the surperficial cathode pole piece with metastable state SEI membrane structure.The coating walking speed of spraying method is 8 ~ 15m/min, and pad specification is 0.01 ~ 0.2mm.Oven temperature 50 ~ 100 DEG C; The coating walking speed of roll coating model is 3 ~ 10m/min, oven temperature 50 ~ 120 DEG C.
Negative pole homogenate slurry is made up of solid matter and water, and the weight portion of each component is:
Graphite 25 ~ 45,
Conductive agent 0.3 ~ 5.0,
Binding agent 0.3 ~ 5.0,
Surfactant 0 ~ 2.0,
Lithium salts 0.0001 ~ 0.01,
Add water and make solid content be 30% ~ 50%.
As preferably, described graphite be selected from Delanium, native graphite, composite graphite, soft carbon, hard carbon one or more; Conductive agent be selected from electrically conductive graphite (comprising SP, KS-6, ECP, carbon nano-tube), vapor-grown carbon fibers one or more; Binding agent is selected from butadiene-styrene rubber (SBR), LA133 aqueous binders a kind of; Surfactant is selected from sodium carboxymethylcellulose (CMC) or polyvinylpyrrolidone (PVP) a kind of; Lithium salts is selected from LiOH, Li
2cO
3, LiF, Li
2c
2o
4, (CH
2oCO
2li)
2, HCOLi, ROCO
2li, ROLi, LiCH
2cH
2oCO
2li, CH
3oCO
2one or more in Li, wherein R represents alkyl.
Negative pole is carried out the preliminary treatment of metastable state SEI film surface-coated by the present invention, avoids lithium ion battery loss part lithium ion in follow-up discharge and recharge activation process, to form SEI film.Now negative terminal surface has been coated with uniform metastable state SEI film, and after battery charging and discharging activation, metastable state SEI film becomes more stable after reforming, and effectively can reduce the irreversible capacity loss of battery simultaneously, promotes the energy density of battery.
Compared with prior art, the invention has the beneficial effects as follows:
(1) method of the present invention is implemented simple, is easy to realize, and scale can apply to the suitability for industrialized production of lithium ion battery completely.
(2) irreversible capacity loss of battery can effectively be reduced after the negative plate obtained by the present invention is applied to lithium ion battery, promote the energy density of battery, the stability of negative plate surface SEI film can be improved simultaneously, improve the cycle performance of battery, effectively can reduce the irreversible capacity loss of battery.
Embodiment
Below by specific embodiment, the present invention is described in further detail.Described in embodiment, raw material is all commercially available, represents with weight portion.
Embodiment 1
(1) by water-soluble to CMC of surfactant (sodium carboxymethylcellulose) 1.5 parts and PVP0.1 part, glue is made,
(2) in glue, add conductive agent SP2 part be mixed and made into conducting resinl,
(3) lithium salts 0.001 part, lithium salts consist of LiOH, Li
2cO
3, (CH
2oCO
2li)
2, mass ratio is 1:1:2, and existing being dissolved in the aqueous solution by lithium salts makes lithium salt solution.In conducting resinl, add Delanium 93.9 parts mix, then add binding agent SBR2.5 part and lithium salt solution, the adjustment viscosity that adds water after mixing is 3500cps and solid content is 38%, obtains homogenate slurry,
(4) after being sieved by homogenate slurry, fineness is 15um, adopts the mode of roller coat in copper foil coating, and coating walking speed is set to 5m/min, till oven temperature arranges 80 ~ 110 DEG C of oven dry.After drying in negative pole coating, namely obtain the negative pole that surface is rich in metastable state SEI film, negative pole surface density is 100g/m
2.
Embodiment 2
(1) by water-soluble for surfactant PVP2 part, glue is made,
(2) in glue, add conductive agent carbon nano-tube 5 parts be mixed and made into conducting resinl,
(3) lithium salts (CH
2oCO
2li)
20.01 part, existing being dissolved in the aqueous solution by lithium salts makes lithium salt solution.In conducting resinl, add 45 parts, soft carbon mix, then add binding agent LA133 aqueous binders 5 parts and lithium salt solution, the adjustment viscosity that adds water after mixing is 5000cps and solid content is 50%, obtains homogenate slurry,
(4) after being sieved by homogenate slurry, fineness is 30um, adopts the mode of spraying in copper foil coating, and coating walking speed is set to 15m/min, and copper foil specification is 0.15mm, till oven temperature arranges 70 ~ 100 DEG C of oven dry.Namely the negative pole that surface is rich in metastable state SEI film is obtained, negative pole surface density 120g/m after drying in negative pole coating
2.
Embodiment 3
(1) by water-soluble for CMC of surfactant 1 part, glue is made,
(2) in glue, add conductive agent VGCF0.3 part be mixed and made into conducting resinl,
(3) lithium salts Li
2cO
30.0001 part, existing being dissolved in the aqueous solution by lithium salts makes lithium salt solution.In conducting resinl, add hard carbon 25 parts mix, then add binding agent SBR0.3 part and lithium salt solution, the adjustment viscosity that adds water after mixing is 2000cps and solid content is 30%, obtains homogenate slurry,
(4) after being sieved by homogenate slurry, fineness is 20um, adopts the mode of roller coat in copper foil coating, and coating walking speed is set to 10m/min, and oven temperature arranges 50 ~ 80 DEG C, till oven dry.Negative pole specification is 0.2mm, after drying in negative pole coating, namely obtain the negative pole that surface is rich in metastable state SEI film, negative pole surface density 110g/m
2.
The metastable state SEI film that embodiment 1 ~ 3 is formed, after battery charging and discharging activation, will reach stable state, reach reduction irreversible capacity loss simultaneously, promotes the energy density of battery.
Claims (9)
1. a negative electrode for lithium ion battery preparation method, it is characterized in that, in negative pole homogenate slurry, add lithium salts, then negative pole homogenate slurry is adopted the mode of spraying or roller coat in conductive foil, namely coating obtains the lithium ion battery negative that surface is rich in metastable state SEI film after drying.
2. a kind of negative electrode for lithium ion battery preparation method according to claim 1, is characterized in that, negative pole homogenate slurry is made up of solid matter and water, and the weight portion of each component is:
Graphite 25 ~ 45,
Conductive agent 0.3 ~ 5.0,
Binding agent 0.3 ~ 5.0,
Surfactant 0 ~ 2.0,
Lithium salts 0.0001 ~ 0.01,
Add water and make solid content be 30% ~ 50%.
3. a kind of negative electrode for lithium ion battery preparation method according to claim 1 and 2, is characterized in that, described graphite be selected from Delanium, native graphite, composite graphite, soft carbon, hard carbon one or more; Conductive agent be selected from electrically conductive graphite, vapor-grown carbon fibers one or more;
Binding agent is selected from butadiene-styrene rubber, LA133 aqueous binders a kind of;
Surfactant is selected from sodium carboxymethylcellulose or polyvinylpyrrolidone a kind of;
Lithium salts is selected from LiOH, Li
2cO
3, LiF, Li
2c
2o
4, (CH
2oCO
2li)
2, HCOLi, ROCO
2li, ROLi, LiCH
2cH
2oCO
2li, CH
3oCO
2one or more in Li, wherein R represents alkyl.
4. a kind of negative electrode for lithium ion battery preparation method according to claim 1, is characterized in that, described preparation method is following steps:
(1) surfactant is water-soluble, make glue,
(2) in glue, add conductive agent and make conducting resinl,
(3) mix after adding graphite in conducting resinl, then add binding agent, lithium salts, add water after mixing and regulate viscosity and solid content, obtain homogenate slurry,
(4) adopt the mode of spraying or roller coat after being sieved by homogenate slurry in conductive foil, namely coating obtains the lithium ion battery negative that surface is rich in metastable state SEI film after drying.
5. a kind of negative electrode for lithium ion battery preparation method according to claim 4, is characterized in that, in step (3), lithium salts is first dissolved in water, adds after making lithium salt solution again.
6. a kind of negative electrode for lithium ion battery preparation method according to claim 4, is characterized in that, in step (3), viscosity is 2000 ~ 5000cps.
7. a kind of negative electrode for lithium ion battery preparation method according to claim 4, is characterized in that, after sieving in step (4), fineness is less than 40um.
8. a kind of negative electrode for lithium ion battery preparation method according to claim 4, it is characterized in that, in step (4) when conducting electricity foil coating, homogenate slurry coating on negative conductive foil, is namely obtained the surperficial cathode pole piece with metastable state SEI membrane structure by the mode of employing spraying or roller coat after oven dry.
9. a kind of negative electrode for lithium ion battery preparation method according to claim 8, is characterized in that, the coating walking speed of spraying method is 8 ~ 15m/min, and pad specification is 0.01 ~ 0.2mm, oven temperature 50 ~ 100 DEG C; The coating walking speed of roll coating model is 3 ~ 10m/min, oven temperature 50 ~ 120 DEG C.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159208A (en) * | 2016-06-29 | 2016-11-23 | 珠海光宇电池有限公司 | Improve method and the cathode of lithium battery of lithium battery first charge-discharge efficiency |
| 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 |
| CN108336354A (en) * | 2018-01-10 | 2018-07-27 | 山东奥冠新能源科技有限公司 | One kind carbon material containing film and preparation method thereof |
| CN108365168A (en) * | 2018-01-10 | 2018-08-03 | 山东奥冠新能源科技有限公司 | Lithium battery cathode plate and its preparation method and application prepared by carbon material containing film |
| CN108417774A (en) * | 2018-02-23 | 2018-08-17 | 江西安驰新能源科技有限公司 | A kind of negative electrode slurry slurry-stirring process and lithium battery with prelithiation effect |
| CN110890516A (en) * | 2018-09-08 | 2020-03-17 | 江西格林德能源有限公司 | Method for prefabricating SEI film of lithium ion battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159208A (en) * | 2016-06-29 | 2016-11-23 | 珠海光宇电池有限公司 | Improve method and the cathode of lithium battery of lithium battery first charge-discharge efficiency |
| 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 |
| CN108336354A (en) * | 2018-01-10 | 2018-07-27 | 山东奥冠新能源科技有限公司 | One kind carbon material containing film and preparation method thereof |
| CN108365168A (en) * | 2018-01-10 | 2018-08-03 | 山东奥冠新能源科技有限公司 | Lithium battery cathode plate and its preparation method and application prepared by carbon material containing film |
| CN108417774A (en) * | 2018-02-23 | 2018-08-17 | 江西安驰新能源科技有限公司 | A kind of negative electrode slurry slurry-stirring process and lithium battery with prelithiation effect |
| CN108417774B (en) * | 2018-02-23 | 2020-05-22 | 江西安驰新能源科技有限公司 | Negative electrode slurry mixing process with pre-lithiation effect and lithium battery |
| CN110890516A (en) * | 2018-09-08 | 2020-03-17 | 江西格林德能源有限公司 | Method for prefabricating SEI film of lithium ion battery |
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Address after: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang District, No. two road, building No. 855, No. Applicant after: Wanxiang 123 Co Ltd Applicant after: Wanxiang Group Corporation Address before: 311215 Xiaoshan economic and Technological Development Zone, Zhejiang, No. two road, building No. 118, No. Applicant before: Universal A 1 System Co., Ltd Applicant before: Wanxiang Group Corporation |
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