CN105845872A - Coating slurry for bonding lithium battery separator and pole piece and preparation method of coating slurry - Google Patents
Coating slurry for bonding lithium battery separator and pole piece and preparation method of coating slurry Download PDFInfo
- Publication number
- CN105845872A CN105845872A CN201610287260.0A CN201610287260A CN105845872A CN 105845872 A CN105845872 A CN 105845872A CN 201610287260 A CN201610287260 A CN 201610287260A CN 105845872 A CN105845872 A CN 105845872A
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- China
- Prior art keywords
- coating
- pole piece
- coating paste
- creating material
- pore creating
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Classifications
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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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
- H01M50/461—Separators, membranes or diaphragms characterised by their combination with electrodes with adhesive layers between electrodes and separators
-
- 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
-
- 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 discloses coating slurry for bonding a lithium battery separator and a pole piece and a preparation method of the coating slurry. The coating slurry coats the lithium battery separator or the pole piece to bond the lithium battery separator and the pole piece, and then is dried; pores are formed in a coating; and the coating slurry is prepared from the following components in parts by weight: 1-10 parts of a pore-forming agent, 1-20 parts of inorganic particles and 3-10 parts of a binder. Uniform distribution of coating pores is achieved through gas release in the high-temperature drying process; and the phenomenon that the slurry blocks a base in the surface coating process of the coating can be effectively avoided, so that the problem that the properties of rate cycle performance and the like are affected due to large internal resistance when the gummed separator or other gummed pole piece is applied to a lithium-ion battery is solved.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of lithium ion battery pore-creating coating material and preparation method thereof.
Background technology
Since the lithium ion battery commercialization nineties in 20th century, due to its have that voltage is high, energy density big, have extended cycle life, the advantage such as memory-less effect, it is widely used in consumption electronic product, currently also it is applied in all kinds of pure electronic, hybrid vehicle as electrokinetic cell, and production capacity demand cumulative year after year.
At present, the production method of lithium ion battery mainly has two kinds, and takeup type is with stacked, and two kinds of techniques are respectively arranged with pluses and minuses.Two ways being contrasted from aspect of performance: the internal resistance of coiled battery is higher, high-multiplying power discharge capacity is less, discharge platform is lower slightly, owing to lug thickness, internal edge space are not fully used, volume and capacity ratio is lower slightly；Laminated battery plate internal resistance is relatively low, and high-multiplying power discharge capacity is more, and multi-pole-piece parallel connection is easier to complete heavy-current discharge in the short time；Discharge platform is high, and internal resistance is less compared with hypopolarization, and inside battery space utilization is abundant, and volume and capacity ratio is higher.For practical operation aspect: takeup type technique produces and controls relatively easy, requires operative employee low it is known that flow process control well and qualified can complete winding after pole piece contraposition；The production of lamination process controls cumbersome, and it is all difficult point that the pole piece detection transhipment statistics of substantial amounts waits；Negative plate is the most not too large relative to the design long, wide of positive plate, so needing operating personnel to have certain operation basis.Integrated comparative in terms of battery performance with actual production two: the advantage of winding is that processing procedure is easy, the advantage of lamination is that battery each side quality is good, advantage for comprehensive two kinds of techniques, at present based on takeup type laminated batteries, barrier film is adhesively fixed by the most topmost operation exactly with positive/negative plate, it is on barrier film, first carry out gluing for the bonding of barrier film Yu pole piece, currently mainly method, then pole piece and gluing barrier film are carried out the compound purpose reaching both bondings of heat.
In general, lithium ion battery includes positive/negative plate, it is clipped in barrier film between the two, electrolyte and seal casinghousing, the diaphragm for lithium ion battery of commercialization at present is generally PP or PE material, in order to improve the thermostability of polyalkene diaphragm to strengthen the security of lithium ion battery, the scheme currently mainly used is to coat, at the single or double of barrier film, the porous active layer that is made up of inorganic particle and binding agent, forms the composite diaphragm of organic and inorganic.For takeup type laminated batteries, its barrier film and positive plate need gluing to realize effectively fixing pole piece, but use the technology mode of barrier film gluing to be easy to bring extra drawback, as caused membrane portions region closed pore to cause the ionic conductivity of whole barrier film to reduce, cause the made internal resistance of cell bigger than normal, final multiplying power and the cycle performance affecting lithium ion battery, so the microcellular structure of barrier film is most important to electrical property and the security performance of battery, for avoiding takeup type laminated batteries barrier film or pole piece at coating viscous glue solution, the problem that inorganic coating etc. cause blocking coated substrate hole etc..
Summary of the invention
It is an object of the invention to: provide a kind of for the lithium battery diaphragm coating paste with pole piece and preparation method thereof that bonds, can apply on lithium ion battery separator or both positive and negative polarity pole piece, it is uniformly distributed at coating paste by pore creating material, its decomposition in dry run is made to discharge gas, it is achieved to form equally distributed hole in the coating.
In order to achieve the above object, the present invention adopts the following technical scheme that
A kind of for the lithium battery diaphragm coating paste with pole piece that bonds, this coating paste is coated on bonding to battery diaphragm and pole piece on battery diaphragm or pole piece, is then dried, and forms hole in coating；Described coating paste is to be prepared from by weight by following components: pore creating material 1 ~ 10 part, inorganic particle 1 ~ 20 part and binding agent 3 ~ 10 parts.
Scheme further, described inorganic particle is aluminum oxide, boehmite, silica；Described binding agent is Kynoar, carboxymethylcellulose calcium, acrylonitrile multipolymer LA133.
Scheme further, the decomposition temperature of described pore creating material is 50 DEG C ~ 80 DEG C, and produces gas after its decomposition.
Further scheme, described pore creating material be particle diameter be ammonium carbonate or the ammonium hydrogen carbonate of 5 ~ 100nm.
Scheme further, described dry temperature, higher than the decomposition temperature of pore creating material, makes pore creating material decompose and produces gas and form hole in the coating.
Ammonium carbonate, ammonium hydrogen carbonate typically can resolve into ammonia and carbon dioxide completely at 60 DEG C.
Another goal of the invention of the present invention is to provide the preparation method of above-mentioned coating paste, and its step is as follows:
(1) pore creating material is dissolved in solvent formation pore creating material solution；
(2) inorganic particle is dispersed in solvent formation inorganic particle liquid；
(3) binding agent is dispersed in solvent formation glue；
(4) pore creating material solution is joined together with glue inorganic particle liquid is stirred mixing, make pore creating material be uniformly distributed, obtain coating paste.
Scheme further, the solvent in described step (1), (2), (3) is water, ethanol, 1-METHYLPYRROLIDONE, acetone or carbonic ester.
The present invention adds pore creating material in coating glue, and by being uniformly distributed in pore creating material slurry so that it is decomposition in dry run and discharge gas, it is achieved form equally distributed hole in the coating.During use, the coating paste present invention prepared is uniformly coated on lithium battery diaphragm or positive/negative plate, it is sticked together with positive/negative plate or barrier film；Then being thermally dried at a temperature of higher than 70 DEG C, coating paste is frozen into coating, and pore creating material therein is thermally decomposed into gas, thus forms uniform hole in the coating.So that barrier film keeps microcellular structure, improve its ionic conductivity, make the battery multiplying power that is finally made and cycle performance unaffected.
In the present invention, the particle diameter of pore creating material is 5 ~ 100nm so that it is adapt to the function of lithium ion battery separator.
So the beneficial effects of the present invention is:
(1) present invention makes pore creating material be dispersed in coating paste, during coating paste is dried, gas solution is at high temperature discharged by the most labile material, thus during coating high-temp is dried, form certain hole, and the even pore distribution that gas produces, to reach the purpose to coating pore-creating.Glue can be prevented effectively from coating procedure, block the phenomenon of barrier film substrate, thus solve gluing barrier film or pole piece for the big problem of lithium ion battery internal resistance, it is to avoid coating porosity is few on battery multiplying power and the impact of cycle performance.
(2) coating paste of the present invention can be applicable on anode pole piece, cathode pole piece or barrier film, meets the pore-creating needs of different coating.
(3) in the present invention, pore creating material can all decompose during high temperature drying and discharges in gaseous form, does not haves residue and the later stage makes the performance impact of battery.
Accompanying drawing explanation
In conjunction with accompanying drawing, the present invention is further described:
Fig. 1 is the distribution schematic diagram of pore creating material in coating paste of the present invention；
Fig. 2 is the dried schematic diagram of coating paste of the present invention.
Detailed description of the invention
Embodiment
1
:
In the round-bottomed flask of 50ml, add the ammonium hydrogen carbonate of 0.1g, be subsequently adding the deionized water of 20ml, under stirring condition, form the solution of clear；Adding the aluminium oxide ceramics dry powder particle of 1g in another flask, the rear 100ml deionized water that adds is disperseed；3rd flask takes the Kynoar PVDF binding agent of 0.5g, by its dispersed with stirring in 50ml organic solvent NMP；After three's Monodispersed is uniform, the ammonium bicarbonate soln of clear, scattered PVDF glue is joined in the flask holding aluminum oxide, after three is sufficiently mixed, i.e. makes coating paste.Then this coating paste is coated on after being connected with pole piece in barrier film substrate carry out 80 DEG C be dried, barrier film can be realized and be connected with pole piece, and form the hole being evenly distributed in the coating.
As it is shown in figure 1, be coated on by coating paste in barrier film substrate 1, pore creating material 3 is uniformly distributed in coating paste 2；After drying, as in figure 2 it is shown, form the pore 4,5 being connected at the two ends of coating.
Embodiment
2
:
In the round-bottomed flask of 50ml, add the ammonium carbonate of 0.1g, be subsequently adding the deionized water of 20ml, under stirring condition, form the solution of clear；Adding the boehmite dry powder particle of 1g in another flask, the rear 100ml deionized water that adds is disperseed；3rd flask takes the carboxyl methyl cellulose binding agent of 0.5g, by its dispersed with stirring in 50ml deionized water；After three's Monodispersed is uniform, the ammonium bicarbonate soln of clear, scattered CMC glue is joined in the flask containing boehmite, after three is sufficiently mixed, i.e. makes coating paste.Then this coating paste is coated on after being connected with pole piece in barrier film substrate carry out 80 DEG C be dried, barrier film can be realized and be connected with pole piece, and form the hole being evenly distributed in the coating.
Embodiment
3
:
In the round-bottomed flask of 150ml, add the ammonium hydrogen carbonate of 0.1g, be subsequently adding the deionized water of 120ml, under stirring condition, form the solution of clear；Adding 1g silica dry powder particle in another flask, the rear 100ml deionized water that adds is disperseed；3rd flask takes the polyacrylic acid PAA of 0.5g, by its dispersed with stirring in 50ml deionized water；Until three's Monodispersed uniformly after, the ammonium bicarbonate soln of clear, scattered PAA glue are joined in the flask containing silica and are stirred, stir until three and i.e. make coating paste after being uniformly dispersed.Then this coating paste is coated on bonding with barrier film in positive plate substrate after carry out 80 DEG C be dried, barrier film can be realized and be connected with positive plate, and form the hole being evenly distributed in the coating.
Embodiment
4
:
In the round-bottomed flask of 150ml, add the ammonium carbonate of 0.1g, be subsequently adding the deionized water of 120ml, under stirring condition, form the solution of clear；Adding 1g silica dry powder particle in another flask, the rear 100ml deionized water that adds is disperseed；3rd flask takes the acrylonitrile multipolymer LA133 of 0.5g, by its dispersed with stirring in 50ml deionized water；Until three's Monodispersed uniformly after, the ammonium bicarbonate soln of clear, scattered LA133 glue are joined in the flask containing silica and are stirred, stir until three and i.e. make coating paste after being uniformly dispersed.Then this coating paste is coated on bonding with barrier film in negative plate substrate after carry out 80 DEG C be dried, barrier film can be realized bonding with negative plate, and form the hole being evenly distributed in the coating.
It should be pointed out that, the professional and technical personnel for making the art, on the premise of without departing from the technology of the present invention principle, be that by the multiple amendment to these embodiments, and these amendments also should be regarded as in the range of the present invention should protect.
Claims (7)
1. the coating paste for bond lithium battery diaphragm and pole piece, it is characterised in that: this coating paste is coated on bonding to battery diaphragm and pole piece on battery diaphragm or pole piece, is then dried it, forms hole in coating；Described coating paste is to be prepared from by weight by following components: pore creating material 1 ~ 10 part, inorganic particle 1 ~ 20 part and binding agent 3 ~ 10 parts.
Coating paste the most according to claim 1, it is characterised in that: described inorganic particle is aluminum oxide, boehmite, silica；Described binding agent is Kynoar, carboxymethylcellulose calcium, acrylonitrile multipolymer LA133.
Coating paste the most according to claim 1, it is characterised in that: the decomposition temperature of described pore creating material is 50 DEG C ~ 80 DEG C, and produces gas after its decomposition.
Coating paste the most according to claim 3, it is characterised in that: described pore creating material be particle diameter be ammonium carbonate or the ammonium hydrogen carbonate of 5 ~ 100nm.
Coating paste the most according to claim 1, it is characterised in that: described dry temperature is higher than the decomposition temperature of pore creating material.
6. the preparation method of coating paste as claimed in claim 1, it is characterised in that: step is as follows:
(1) pore creating material is dissolved in solvent formation pore creating material solution；
(2) inorganic particle is dispersed in solvent formation inorganic particle liquid；
(3) binding agent is dispersed in solvent formation glue；
(4) pore creating material solution is joined together with glue inorganic particle liquid is stirred mixing, make pore creating material be uniformly distributed, obtain coating paste.
Preparation method the most according to claim 6, it is characterised in that: the solvent in described step (1), (2), (3) is water, ethanol, 1-METHYLPYRROLIDONE, acetone or carbonic ester.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610287260.0A CN105845872A (en) | 2016-05-04 | 2016-05-04 | Coating slurry for bonding lithium battery separator and pole piece and preparation method of coating slurry |
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| CN201610287260.0A CN105845872A (en) | 2016-05-04 | 2016-05-04 | Coating slurry for bonding lithium battery separator and pole piece and preparation method of coating slurry |
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681113A (en) * | 2016-08-01 | 2018-02-09 | 宁德时代新能源科技股份有限公司 | Positive plate, preparation method thereof and secondary battery |
| CN108321342A (en) * | 2018-01-04 | 2018-07-24 | 河南惠强新能源材料科技股份有限公司 | A kind of lithium battery diaphragm coating paste and preparation method thereof having iron ion adsorption function |
| CN109860480A (en) * | 2018-12-29 | 2019-06-07 | 桑顿新能源科技有限公司 | A kind of gel state lithium ion battery diaphragm and preparation method thereof |
| CN110380002A (en) * | 2019-06-03 | 2019-10-25 | 江西力能新能源科技有限公司 | A kind of boehmite/alumina composite lithium ion battery coating pole piece |
| WO2020107286A1 (en) * | 2018-11-28 | 2020-06-04 | 湖南中锂新材料有限公司 | Porous coating film, and preparation method therefor and application thereof |
| CN111564593A (en) * | 2020-06-04 | 2020-08-21 | 江苏星源新材料科技有限公司 | Diaphragm, diaphragm roll, battery core and power lithium battery |
| CN111725511A (en) * | 2020-06-29 | 2020-09-29 | 东莞市魔方新能源科技有限公司 | Lithium ion secondary battery pole piece and lithium ion secondary battery |
| CN111732867A (en) * | 2020-06-29 | 2020-10-02 | 蜂巢能源科技有限公司 | Coating slurry, coating, lithium ion battery and application of coating slurry and coating |
| CN111965092A (en) * | 2020-07-17 | 2020-11-20 | 重庆市紫建电子股份有限公司 | Method and device for detecting dust particles of pole piece |
| WO2021109685A1 (en) * | 2019-12-06 | 2021-06-10 | 华中科技大学 | Preparation method and product of lithium ion battery pole piece with vertical pore channel structure |
| CN113540686A (en) * | 2020-04-20 | 2021-10-22 | 河北金力新能源科技股份有限公司 | Functional diaphragm for lithium-sulfur battery and preparation method thereof |
| CN114267890A (en) * | 2021-12-28 | 2022-04-01 | 广东国光电子有限公司 | Positive pole piece and preparation method and application thereof |
| CN114464816A (en) * | 2022-04-12 | 2022-05-10 | 瑞浦能源有限公司 | Current collector with pore-forming functional coating, pole piece and lithium ion battery |
| CN114597584A (en) * | 2022-03-24 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Lithium ion battery diaphragm with charging protection function and preparation method thereof |
| CN114639922A (en) * | 2022-04-07 | 2022-06-17 | 湖北允升科技工业园有限公司 | Lithium ion battery diaphragm and lithium ion battery |
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| CN102916149A (en) * | 2012-09-26 | 2013-02-06 | 东莞市创明电池技术有限公司 | Micropore membrane of lithium battery and preparation technique for micropore membrane |
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Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681113A (en) * | 2016-08-01 | 2018-02-09 | 宁德时代新能源科技股份有限公司 | Positive plate, preparation method thereof and secondary battery |
| CN107681113B (en) * | 2016-08-01 | 2020-07-28 | 宁德时代新能源科技股份有限公司 | Positive plate, preparation method thereof and secondary battery |
| CN108321342A (en) * | 2018-01-04 | 2018-07-24 | 河南惠强新能源材料科技股份有限公司 | A kind of lithium battery diaphragm coating paste and preparation method thereof having iron ion adsorption function |
| WO2020107286A1 (en) * | 2018-11-28 | 2020-06-04 | 湖南中锂新材料有限公司 | Porous coating film, and preparation method therefor and application thereof |
| CN109860480A (en) * | 2018-12-29 | 2019-06-07 | 桑顿新能源科技有限公司 | A kind of gel state lithium ion battery diaphragm and preparation method thereof |
| CN110380002A (en) * | 2019-06-03 | 2019-10-25 | 江西力能新能源科技有限公司 | A kind of boehmite/alumina composite lithium ion battery coating pole piece |
| WO2021109685A1 (en) * | 2019-12-06 | 2021-06-10 | 华中科技大学 | Preparation method and product of lithium ion battery pole piece with vertical pore channel structure |
| US11183677B2 (en) | 2019-12-06 | 2021-11-23 | Huazhong University Of Science And Technology | Preparation method and product of lithium-ion battery electrode sheet with vertical vent structures |
| CN113540686A (en) * | 2020-04-20 | 2021-10-22 | 河北金力新能源科技股份有限公司 | Functional diaphragm for lithium-sulfur battery and preparation method thereof |
| CN111564593A (en) * | 2020-06-04 | 2020-08-21 | 江苏星源新材料科技有限公司 | Diaphragm, diaphragm roll, battery core and power lithium battery |
| CN111725511B (en) * | 2020-06-29 | 2021-11-30 | 东莞市魔方新能源科技有限公司 | Lithium ion secondary battery pole piece and lithium ion secondary battery |
| CN111732867A (en) * | 2020-06-29 | 2020-10-02 | 蜂巢能源科技有限公司 | Coating slurry, coating, lithium ion battery and application of coating slurry and coating |
| CN111725511A (en) * | 2020-06-29 | 2020-09-29 | 东莞市魔方新能源科技有限公司 | Lithium ion secondary battery pole piece and lithium ion secondary battery |
| CN111732867B (en) * | 2020-06-29 | 2022-07-26 | 蜂巢能源科技股份有限公司 | Coating slurry, coating, lithium ion battery and application of coating slurry and coating |
| CN111965092A (en) * | 2020-07-17 | 2020-11-20 | 重庆市紫建电子股份有限公司 | Method and device for detecting dust particles of pole piece |
| CN114267890A (en) * | 2021-12-28 | 2022-04-01 | 广东国光电子有限公司 | Positive pole piece and preparation method and application thereof |
| CN114597584A (en) * | 2022-03-24 | 2022-06-07 | 河北金力新能源科技股份有限公司 | Lithium ion battery diaphragm with charging protection function and preparation method thereof |
| CN114597584B (en) * | 2022-03-24 | 2024-02-06 | 河北金力新能源科技股份有限公司 | Lithium ion battery diaphragm with charging protection function and preparation method thereof |
| CN114639922A (en) * | 2022-04-07 | 2022-06-17 | 湖北允升科技工业园有限公司 | Lithium ion battery diaphragm and lithium ion battery |
| CN114464816A (en) * | 2022-04-12 | 2022-05-10 | 瑞浦能源有限公司 | Current collector with pore-forming functional coating, pole piece and lithium ion battery |
| CN114464816B (en) * | 2022-04-12 | 2022-07-12 | 瑞浦兰钧能源股份有限公司 | Current collector with pore-forming functional coating, pole piece and lithium ion battery |
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Application publication date: 20160810 |