CN105449156A - Preparation method of negative electrode of lithium-ion battery - Google Patents
Preparation method of negative electrode of lithium-ion battery Download PDFInfo
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- CN105449156A CN105449156A CN201510136806.8A CN201510136806A CN105449156A CN 105449156 A CN105449156 A CN 105449156A CN 201510136806 A CN201510136806 A CN 201510136806A CN 105449156 A CN105449156 A CN 105449156A
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- ion battery
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Abstract
The invention relates to the technical field of lithium-ion batteries, aims at solving the problem of irreversible capacity loss of an existing lithium-ion battery, and provides a preparation method of a negative electrode of a lithium-ion battery. The method comprises the following steps: coating a conductive foil with negative homogenate slurry for the first time; carrying out secondary dip-coating after soaking in a lithium salt solution; and drying the conductive foil to obtain the negative electrode, rich in a semi-stable state SEI film on the surface, of the lithium-ion battery. The semi-stable state SEI film is firstly formed on the surface of the negative electrode; and the SEI film is formed without consuming lithium ions of the negative electrode in subsequent charge and discharge processes, 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 lithium ion battery negative.
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 preparation method of lithium ion battery negative, 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: the preparation method of negative pole described in a kind of preparation method of lithium ion battery negative be by negative pole homogenate slurry after conductive foil the 1st time coating, carry out the 2nd dip-coating after infiltrating in lithium salt solution again, after oven dry, namely obtain the lithium ion battery negative that surface is rich in metastable state SEI film.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, add water after mixing and regulate viscosity and solid content, obtain homogenate slurry,
As preferably, solid content is 30 ~ 50%, and the viscosity of homogenate slurry is 2000 ~ 5000cps.
(4) after being sieved by homogenate slurry after conductive foil the 1st coating, then carry out the 2nd dip-coating after infiltrating in lithium salt solution, after oven dry, namely obtain the lithium ion battery negative that surface is rich in metastable state SEI film.
As preferably, lithium salts is first dissolved in water, adds after making lithium salt solution again.The use amount of solvent is the amount making solute dissolves.
As preferably, conductive foil selects conventional copper foil,
As preferably, after sieving, fineness is less than 40um.
As preferably, when conducting electricity foil coating, adopt the mode of spraying or roller coat to be coated on negative conductive foil by homogenate slurry first time, in lithium salt solution, then carry out dip-coating completed secondary dip-coating, after oven dry, namely obtain 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.The walking speed of dip coating manner is 3 ~ 10m/min, oven temperature 50 ~ 110 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,
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, and the use amount of lithium salts is 0.0001 ~ 0.01% of solid matter quality in homogenate slurry.
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.
Accompanying drawing explanation
Fig. 1 is after being sieved by homogenate slurry after conductive foil coating, then carries out the schematic diagram of the 2nd dip-coating after infiltrating in lithium salt solution.
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) in conducting resinl, add Delanium 93.9 parts mix, the adjustment viscosity that adds water after then adding the mixing of binding agent SBR2.5 part is 3500cps and solid content is 38%, obtains homogenate slurry,
(4) 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.
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.Then the 2nd dip-coating is carried out after being infiltrated in lithium salt solution by the negative pole paillon foil after first time coating again, dip-coating walking speed is set to 3m/min, till oven temperature arranges 50 ~ 90 DEG C of oven dry, 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) in conducting resinl, add 45 parts, soft carbon to mix, then add binding agent LA133 aqueous binders 5 parts, the adjustment viscosity that adds water after mixing is 5000cps and solid content is 50%, obtains homogenate slurry,
(4) lithium salts (CH
2oCO
2li)
20.01 part, existing being dissolved in the aqueous solution by lithium salts makes lithium salt solution.
After being sieved by homogenate slurry, fineness is 30um, the mode of spraying is adopted in copper foil coating, coating walking speed is set to 15m/min, copper foil specification is 0.15mm, till oven temperature arranges 70 ~ 100 DEG C of oven dry, carries out the 2nd dip-coating after then being infiltrated in lithium salt solution by the negative pole paillon foil after first time coating again, dip-coating walking speed is set to 5m/min, namely oven temperature obtains the negative pole that surface is rich in metastable state SEI film, negative pole surface density 120g/m till arranging 100 ~ 110 DEG C of oven dry after oven dry
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) in conducting resinl, add hard carbon 25 parts mix, then add binding agent SBR0.3 part, the adjustment viscosity that adds water after mixing is 2000cps and solid content is 30%, obtains homogenate slurry,
(4) lithium salts Li
2cO
30.0001 part, existing being dissolved in the aqueous solution by lithium salts makes lithium salt solution.
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.Then the 2nd dip-coating is carried out after being infiltrated in lithium salt solution by the negative pole paillon foil after first time coating again, dip-coating walking speed is set to 10m/min, till oven temperature arranges 70 ~ 90 DEG C of oven dry, negative pole specification is 0.2mm, namely the negative pole that surface is rich in metastable state SEI film is obtained, negative pole surface density 110g/m after oven dry
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 (10)
1. the preparation method of a lithium ion battery negative, it is characterized in that, by negative pole homogenate slurry after conductive foil the 1st coating, then carry out the 2nd dip-coating after infiltrating in lithium salt solution, after oven dry, namely obtain the lithium ion battery negative that surface is rich in metastable state SEI film.
2. the preparation method of a kind of lithium ion battery negative 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,
Add water and make solid content be 30% ~ 50%.
3. the preparation method of a kind of lithium ion battery negative according to claim 1, is characterized in that, the use amount of lithium salts is 0.0001 ~ 0.01% of solid matter quality in homogenate slurry.
4. the preparation method of a kind of lithium ion battery negative according to Claims 2 or 3, 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.
5. the preparation method of a kind of lithium ion battery negative 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, add water after mixing and regulate viscosity and solid content, obtain homogenate slurry,
(4) after being sieved by homogenate slurry after conductive foil the 1st coating, then carry out the 2nd dip-coating after infiltrating in lithium salt solution, after oven dry, namely obtain the lithium ion battery negative that surface is rich in metastable state SEI film.
6. the preparation method of a kind of lithium ion battery negative according to claim 5, is characterized in that, in step (3), viscosity is 2000 ~ 5000cps.
7. the preparation method of a kind of lithium ion battery negative according to claim 5, is characterized in that, after sieving in step (4), fineness is less than 40um.
8. the preparation method of a kind of lithium ion battery negative according to claim 5, is characterized in that, lithium salt solution, for be first dissolved in water by lithium salts, makes lithium salt solution.
9. the preparation method of a kind of lithium ion battery negative according to claim 5, is characterized in that, when conducting electricity foil the 1st coating, adopt the mode of spraying or roller coat, the walking speed of spraying method is 8 ~ 15m/min, and pad specification is 0.01 ~ 0.2mm, oven temperature 50 ~ 100 DEG C; The walking speed of roll coating model is 3 ~ 10m/min, oven temperature 50 ~ 120 DEG C.
10. the preparation method of a kind of lithium ion battery negative according to claim 5, is characterized in that, the cathode pole piece after the 1st coating, then carries out the 2nd dip-coating, dip-coating walking speed 3 ~ 10m/min, oven temperature 50 ~ 110 DEG C after infiltrating in lithium salt solution.
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| CN201510136806.8A CN105449156A (en) | 2015-03-27 | 2015-03-27 | Preparation method of negative electrode of lithium-ion battery |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520978A (en) * | 2017-03-13 | 2018-09-11 | 万向二三股份公司 | A kind of lithium ion battery benefit lithium technique |
| CN108736056A (en) * | 2017-04-20 | 2018-11-02 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium metal interface protection structure and its preparation and application |
| CN110085806A (en) * | 2019-04-30 | 2019-08-02 | 湖北锂诺新能源科技有限公司 | Silicon-carbon cathode and preparation method thereof and lithium ion battery |
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| US20140027292A1 (en) * | 2011-04-06 | 2014-01-30 | Electricite De France | Lithium-ion battery precursor including a sacrificial lithium electrode and a negative textile conversion electrode |
| CN103855358A (en) * | 2012-12-07 | 2014-06-11 | 华为技术有限公司 | Lithium battery negative electrode as well as preparation method thereof, lithium battery and application |
| CN104201384A (en) * | 2014-04-19 | 2014-12-10 | 东风商用车有限公司 | Lithium ion battery negative pole piece and manufacturing method thereof |
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2015
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Patent Citations (4)
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|---|---|---|---|---|
| CN101016412A (en) * | 2007-03-06 | 2007-08-15 | 中南大学 | Method of preparing lithium salt doping state polyaniline electrode material for super capacitor |
| US20140027292A1 (en) * | 2011-04-06 | 2014-01-30 | Electricite De France | Lithium-ion battery precursor including a sacrificial lithium electrode and a negative textile conversion electrode |
| CN103855358A (en) * | 2012-12-07 | 2014-06-11 | 华为技术有限公司 | Lithium battery negative electrode as well as preparation method thereof, lithium battery and application |
| CN104201384A (en) * | 2014-04-19 | 2014-12-10 | 东风商用车有限公司 | Lithium ion battery negative pole piece and manufacturing method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108520978A (en) * | 2017-03-13 | 2018-09-11 | 万向二三股份公司 | A kind of lithium ion battery benefit lithium technique |
| CN108520978B (en) * | 2017-03-13 | 2020-07-31 | 万向一二三股份公司 | Lithium ion battery lithium supplementing process |
| CN108736056A (en) * | 2017-04-20 | 2018-11-02 | 中国科学院宁波材料技术与工程研究所 | A kind of lithium metal interface protection structure and its preparation and application |
| CN108736056B (en) * | 2017-04-20 | 2020-12-11 | 中国科学院宁波材料技术与工程研究所 | Lithium metal interface protection structure and preparation and application thereof |
| CN110085806A (en) * | 2019-04-30 | 2019-08-02 | 湖北锂诺新能源科技有限公司 | Silicon-carbon cathode and preparation method thereof and 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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Application publication date: 20160330 |