CN102206420A - Composition for battery diaphragm, battery diaphragm and lithium-ion secondary battery - Google Patents
Composition for battery diaphragm, battery diaphragm and lithium-ion secondary battery Download PDFInfo
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- CN102206420A CN102206420A CN2010101393279A CN201010139327A CN102206420A CN 102206420 A CN102206420 A CN 102206420A CN 2010101393279 A CN2010101393279 A CN 2010101393279A CN 201010139327 A CN201010139327 A CN 201010139327A CN 102206420 A CN102206420 A CN 102206420A
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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
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Abstract
The invention provides a composition for a battery diaphragm, containing modified polysiloxane, a solvent and an inorganic filler, wherein the modified polysiloxane has a structure shown as a formula 1. The invention also provides a battery diaphragm prepared from the composition and a lithium-ion secondary battery containing the battery diaphragm. The composition for the battery diaphragm provided by the invention contains the modified polysiloxane shown as the formula 1, the main chain segment of the modified polysiloxane is an inorganic silica chain segment, and the modified polysiloxane has favorable compatibility with the inorganic filler so that anode and cathode circuit breaking can be still ensured when a porous polyolefin film shrinks due to overhigh temperature and the safety performance of the battery is improved; in addition, a lateral group ethyoxyl repeating unit of the modified polysiloxane can enhance the affinity of lithium ions and reduce the internal resistance of the diaphragm, and a lateral group cinnamoyl group can be cured and crosslinked without any initiator or being heated, thus the cycle performance of the battery is ensured effectively.
Description
Technical field
The present invention relates to field of lithium ion secondary, relate in particular to a kind of battery diaphragm composition, a kind of battery diaphragm and a kind of lithium-ion secondary cell.
Background technology
Lithium-ion secondary cell has high-energy-density, high-voltage, pollution-free, characteristics such as containing metal lithium, cycle life height, memory-less effect, charge velocities be not fast.Along with improving constantly of people's demand, need lithium-ion secondary cell to have the performance of higher capacity and Geng Gao.
In the lithium-ion secondary cell,, be easy to generate dendrite in the working cycle, pierce through barrier film and cause short circuit along with the increase of cell container and discharge-rate; In addition, the lithium ion battery separator that uses mainly is a polyalkene diaphragm at present, and during battery generation internal short-circuit, local a large amount of heatings can make polyalkene diaphragm produce thermal contraction, and short-circuited region enlarges, and causes battery explosion easily, and the safety performance of battery is lower.
In order to improve the security of battery, prior art is improved barrier film.For example, WO2009069928 discloses a kind of preparation method of battery diaphragm, adopt the oligosiloxane of acrylate ended as tackiness agent in this method, to be coated to polyalkene diaphragm or nonwoven surface after this tackiness agent and the mineral filler mixing and ball milling, thermal initiation curing promptly obtains battery diaphragm again.This membranous thermal safety is improved, and the cycle charge-discharge capability retention is also higher; But have following defective: (1) because the crosslinking curing of acrylate group need add initiator, and cost is higher, and complete reaction and residual initiator reduces cycle performance of battery not; (2) temperature is higher during thermofixation, makes barrier film produce shrinkage, reduces its porosity, and the ion guide passband reduces, so cycle performance of battery reduces; (3) acrylate Raolical polymerizable condition harshness during thermofixation, industrializing implementation difficulty height.
Summary of the invention
The invention solves the technical problem that the battery diaphragm security is low, cycle performance of battery is relatively poor that exists in the prior art.
The invention provides a kind of battery diaphragm composition, contain modified polyorganosiloxane, solvent and mineral filler, described modified polyorganosiloxane has structure shown in the formula 1:
Formula 1
Wherein, n is 30-100, and m is 30-100, and x is 1-5.
The present invention also provides a kind of battery diaphragm, and described battery diaphragm obtains by also solidifying with composition at porous polyolefin membrane coating on both sides barrier film, and wherein, described barrier film composition is a battery diaphragm composition provided by the invention.
The present invention also provides a kind of lithium-ion secondary cell, this battery comprises battery container, electrode group and electrolytic solution, electrode group and electrolytic solution are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, wherein, described barrier film is a battery diaphragm provided by the invention.
Battery diaphragm of the present invention is with containing the modified polyorganosiloxane shown in the formula 1 in the composition, the main chain section is inorganic silica segment, mineral filler can be evenly distributed on the porous polyolefin membrane, when temperature is too high when making porous polyolefin membrane generation shrinkage, mineral filler can guarantee that still positive and negative electrode keeps opening circuit, thereby improves the safety performance of battery; In addition; the side group oxyethyl group repeating unit of the modified polyorganosiloxane shown in the formula 1 is strengthened the affinity of lithium ion in diaphragm material and the electrolytic solution; help quickening passing through of lithium ion; reduce the barrier film internal resistance; and another side group cinnamoyl group need not initiator need not the heating curing cross-linked can take place; can effectively guarantee the cycle performance of battery, the industrial implementation condition is easy.
Embodiment
The invention provides a kind of battery diaphragm composition, contain modified polyorganosiloxane, solvent and mineral filler, described modified polyorganosiloxane has structure shown in the formula 1:
Formula 1
Wherein, n is 30-100, and m is 30-100, and x is 1-5.
Among the present invention, described modified polyorganosiloxane has structure shown in the formula 1, and described modified polyorganosiloxane can directly be commercially available, and can adopt also that disclosed method prepares in the prior art, for example can adopt the preparation of US2005271948A1 disclosed method.Particularly, may further comprise the steps: (1) is grafted to ethylene glycol monoallyl ether and low polyoxyethylene glycol-single first-mono allyl ether on the polymethyl hydrogen siloxane macromolecular chain under catalyst Pt (0) condition; (2) under the catalyst of triethylamine condition, the hydroxyl with side chain carries out esterification with cinnamyl chloride again, can obtain the modified polyorganosiloxane of 1 formula of formula; Building-up reactions mechanism is as shown in the formula shown in 2.Wherein two-step reaction all carries out in solvent, and the solvent that the reaction of (1) step is adopted is a toluene, and the solvent that (2) step adopted is a tetrahydrofuran (THF).
Described battery diaphragm is with in the composition, is benchmark with the modified polyorganosiloxane of 1 weight part, and the content of solvent is the 35-45 weight part, and the content of mineral filler is the 8-12 weight part; Under the preferable case, the content of solvent is the 38-42 weight part, and the content of mineral filler is the 9-11 weight part.
The various easy volatile solvent that described solvent is used always for those skilled in the art for example can be selected from a kind of in acetone, tetrahydrofuran (THF), the toluene.
Formula 2
Described mineral filler is inorganic oxide and/or inorganic salt.According to composition provided by the invention, in the preferred case, described mineral filler has good oleophilic properties and bigger specific surface area, and is not dissolved in the organic electrolyte.The specific surface area of mineral filler is preferably 1-4000m
2/ g, more preferably 5-50m
2/ g.In order to make composition in porous polyolefin rete the more even and solid particulate easier dispersion of battery diaphragm of the present invention with composition, under the preferable case, the median size of mineral filler is 100-1000nm, more preferably 300-500nm.
According to composition provided by the invention, in the preferred case, be in the oxide compound of aluminium, zirconium, magnesium, calcium, titanium, silicon, barium, zinc one or more as the inorganic oxide of mineral filler, inorganic salt are one or more in vitriol, silicate, carbonate and the titanate of aluminium, zirconium, magnesium, calcium, titanium, barium, zinc.For example, inorganic oxide as mineral filler of the present invention is one or more in calcium oxide, magnesium oxide, aluminum oxide, zirconium white, zinc oxide, the titanium oxide, and the inorganic salt as mineral filler of the present invention are one or more in kaolin, asbestos, Magnesium Silicate q-agent, Calucium Silicate powder, pure aluminium silicate, lime carbonate, barium sulfate and the barium titanate.
Battery diaphragm of the present invention comprises with the preparation of compositions method modified polyorganosiloxane, the mineral filler shown in the formula 1 is mixed that ball milling to the required particle diameter that stirs gets final product in solvent.
The present invention also provides a kind of battery diaphragm, and battery diaphragm is characterized in that by obtaining with composition and curing at porous polyolefin membrane coating on both sides barrier film described barrier film composition is a battery diaphragm composition provided by the invention.
Described porous polyolefin membrane is the common various polyolefine that directly are used as battery diaphragm of those skilled in the art, for example polypropylene (PP), polyethylene terephthalate (PET) or polyethylene (PE).The aperture of described porous polyolefin membrane is 50-300nm, and porosity is 15-50%, and thickness is 10-40 μ m.
Among the present invention, described battery diaphragm solidifies then and can obtain by at existing porous polyolefin membrane coating on both sides battery diaphragm composition of the present invention.Wherein, described battery diaphragm is 1-50g/cm with the consumption of composition
2The various coating methods that the mode of described coating is used always for those skilled in the art, for example dip-coating, brushing, roller coating, but be not limited to this.Described curing can be adopted ultraviolet light polymerization, and condition of cure comprises: solidification value is 20-60 ℃, and be 5-30min set time.Under the preferable case, the ultraviolet light polymerization process is carried out under the state of vacuumizing, and in time takes the evaporable solvent away.
Be grafted with cinnamoyl on the side chain of modified polyorganosiloxane, the crosslinking reaction shown in the following formula 3 can take place in the cinnyl group under UV-light (UV) condition; Wherein "---" represents the polysiloxane backbone section.
Formula 3
Crosslinking reaction shown in the following formula 3 need not initiator and need not heating, alkene can take place become ring crosslinked, and crosslinking degree is higher, make the modified polyorganosiloxane completion of cure that the present invention adopts, evenly attached to the porous polyolefin membrane surface, and with the combining closely of porous polyolefin membrane; On the mineral filler uniform distribution porous polyolefin membrane, when temperature is too high when making porous polyolefin membrane generation shrinkage, mineral filler can guarantee that still positive and negative electrode keeps opening circuit, thereby improves the safety performance of battery.
In addition; the side group oxyethyl group repeating unit of the modified polyorganosiloxane that the present invention adopts is strengthened the affinity of lithium ion in diaphragm material and the electrolytic solution; help quickening passing through of lithium ion; reduce the barrier film internal resistance; and another side group cinnamoyl group need not initiator need not the heating curing cross-linked can take place, can effectively guarantee the cycle performance of battery.
The present invention also provides a kind of lithium-ion secondary cell, this battery comprises battery container, electrode group and electrolytic solution, electrode group and electrolytic solution are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, wherein, described barrier film is a battery diaphragm provided by the invention.
According to lithium-ion secondary cell provided by the invention, there is no particular limitation to positive pole, negative pole and the battery container of polymer battery and their structural relation in the present invention, and described positive pole and negative pole can be used for the various positive poles and the negative pole of polymer battery for art technology is known.Among the present invention, the thickness of described battery diaphragm is the 15-60 micron.
For example, described positive pole comprises plus plate current-collecting body and loads on positive electrode material on the plus plate current-collecting body.Described plus plate current-collecting body can be selected from aluminium foil, Copper Foil, nickel plated steel strip or Punching steel strip; Positive electrode material comprises positive active material and anodal binding agent, and wherein positive active material can be selected from LiCoO
2, LiNiO
2, LiMn
2O
4, LiFePO
4In one or more, anodal binding agent can be selected from fluorine resin and/or polyolefin compound, as in polyvinylidene difluoride (PVDF) (PVDF), polytetrafluoroethylene (PTFE) or the styrene-butadiene rubber(SBR) (SBR) one or more.Described anodal content with binding agent is the 0.01-8 weight % of positive active material, is preferably 1-5 weight %.
Described negative pole comprises negative current collector and the negative electrode material layer that is coated on this negative current collector.Described negative electrode material layer comprises the conductive agent that negative electrode active material, negative pole binding agent and selectivity contain.Wherein, negative electrode active material can be selected from lithium metal, lithium alloy, graphite, carbon fiber, hard carbon, aluminosilicate alloy material, iron phosphide; Conductive agent is selected from one or more in conductive carbon black, nickel powder, the copper powder; The negative pole binding agent is selected from one or more in polyvinyl alcohol, tetrafluoroethylene, Walocel MT 20.000PV (CMC), the styrene-butadiene rubber(SBR) (SBR).Described negative pole is the 0.5-8 weight % of negative electrode active material with the content of binding agent, is preferably 2-5 weight %.With the negative material is benchmark, and the content of conductive agent is generally 0.1-12 weight %.
The preparation method of described positive pole and negative pole can adopt the whole bag of tricks known in the field.
Described electrolytic solution is nonaqueous electrolytic solution, i.e. the solution that forms in non-aqueous solvent of electrolyte lithium salt.Described electrolyte lithium salt can be selected from LiPF
6, LiClO
4, LiBF
4, LiAsF
6, LiSiF
6, LiB (C
6H
5)
4, LiCl, LiBr, LiAlCl
4, LiC (SO
2CF
3)
3, LiCH
3SO
3, LiN (SO
2CF
3)
2In one or more.Non-aqueous solvent can adopt one or more in NSC 11801 (EC), propylene carbonate (PC), methylcarbonate (DMC), vinylene carbonate (VC), the diethyl carbonate (DEC).Under the preferable case, non-aqueous solvent adopts the mixed solvent of EC, PC and DEC, and more preferably the volume ratio of EC under the situation: PC: DEC is 3: 2: 5.In the described nonaqueous electrolytic solution, the concentration of electrolyte lithium salt is the 0.1-2 mol, is preferably the 0.8-1.2 mol.
According to lithium-ion secondary cell provided by the invention, the preparation method of this battery is as well known to those skilled in the art, in general, the preparation method of this battery comprises the electrode group is inserted in the battery case, add electrolytic solution, sealing obtains lithium-ion secondary cell then.Wherein, the method for sealing, the consumption of electrolytic solution is conventionally known to one of skill in the art.
Below in conjunction with embodiment the present invention is further detailed.The raw material that adopts all is commercially available in embodiment and the Comparative Examples.
Embodiment 1
(1) preparation of modified polyorganosiloxane: adopt US2005271948A1 embodiment disclosed method to prepare the modified polyorganosiloxane shown in the formula 1 of present embodiment, wherein, n is 60, and m is 50, and x is 3.
(2) modified polyorganosiloxane with step (1) preparation is dissolved among the THF, forms the solution of 2.5wt%; Add BaTiO
3, BaTiO
3With the weight ratio of modified polyorganosiloxane be 10: 1; After mixing, change ball mill over to and carry out ball milling, to BaTiO
3Median size 400nm obtains the barrier film slurry.
(3) adopt the immersion coating method, coat the barrier film slurry that step (2) obtains in PE film (thickness 18 μ m, porosity 45%) both sides, coating thickness is 3 μ m; Place under the 100W high voltage mercury lamp, shine, irradiation distance 10cm, irradiation time 10min with the UV-light of wavelength 365nm.
By above-mentioned steps, obtain the battery diaphragm of present embodiment, be designated as G1.
Embodiment 2-5
Adopt the step identical with embodiment 1 to prepare the battery diaphragm of embodiment 2-5, difference is that the component of barrier film composition and content are as shown in table 1 below:
Table 1
Embodiment 6-10
Use the battery diaphragm G1-G5 that obtains among the embodiment 1-5 respectively, use LiCoO
2As positive pole, graphite uses the LiPF of 1mol/L as negative pole
6Solution is as electrolytic solution, and it is the mixing solutions of EC/PC/DEC=30/20/50 that solvent adopts volume ratio, and positive and negative electrode is placed the battery diaphragm both sides, be wound into sheet, cut, the material of winding is put into encapsulating housing to certain size, obtain lithium-ion secondary cell, be designated as S1-S5.
Comparative Examples 1
Adopt WO2009069928 embodiment 1 disclosed method to prepare the barrier film DG1 and the lithium-ion secondary cell DS1 of this Comparative Examples.
Performance test:
1, battery diaphragm test:
Adopt mean pore size and the porosity of SEM and mercury injection apparatus test battery barrier film G1-G5 and DG1, test result is as shown in table 2.
Table 2
| Battery diaphragm | G1 | G2 | G3 | G4 | G5 | DG1 |
| Mean pore size (nm) | 420 | 350 | 450 | 430 | 410 | 400 |
| Porosity (%) | 42 | 33 | 43 | 44 | 40 | 40 |
2, cycle performance of battery test
Lithium-ion secondary cell S1-S5 and DS1 are carried out the charge-discharge performance test, carry out the charge and discharge cycles experiment of 1C/2C under 60 ℃, the test loop number of times is the capacity surplus ratio (%) after 100,200,300 times.Test result is as shown in table 3.
Table 3
| Lithium-ion secondary cell | 100 circulations (%) | 200 circulations (%) | 300 circulations (%) |
| S1 | 99 | ?96 | ?94 |
| S2 | 98 | ?94 | ?93 |
| S3 | 97 | ?93 | ?90 |
| S4 | 99 | ?95 | ?91 |
| S5 | 96 | ?92 | ?90 |
| DS1 | 98 | ?95 | ?92 |
3, battery safety test
Lithium-ion secondary cell S1-S5 and DS1 are placed airtight baking oven, carry out the high temperature safe test, its test result is as shown in table 4, and wherein " OK " expression is by test, and " NG " expression takes place on fire or blast.150 ℃/2hr represents that polymer battery toasted 2 hours down at 150 ℃.
Table 4
| Lithium-ion secondary cell | 150℃/2hr | 150℃/2hr | 160℃/1hr | 160℃/2hr |
| S1 | OK | OK | OK | OK |
| S2 | OK | OK | OK | NG |
| S3 | OK | OK | OK | NG |
| S4 | OK | OK | OK | NG |
| S5 | OK | OK | OK | OK |
| DS1 | OK | OK | NG | NG |
By last table 3-4 as can be seen, adopt the lithium-ion secondary cell of battery diaphragm provided by the invention, keeping under the better cycle performance prerequisite, safety performance obviously is better than various lithium-ion secondary cell of the prior art.More as can be seen, when the content of modified polyorganosiloxane, mineral filler and solvent was in preferable range of the present invention in the battery separator composition of the present invention, the cycle performance and the safety performance of lithium-ion secondary cell were better from the test result of S1-S3.
Claims (12)
1. a battery diaphragm composition contains modified polyorganosiloxane, solvent and mineral filler, and described modified polyorganosiloxane has structure shown in the formula 1:
Formula 1
Wherein, n is 30-100, and m is 30-100, and x is 1-5.
2. battery diaphragm composition according to claim 1 is characterized in that, described battery diaphragm is with in the composition, is benchmark with the modified polyorganosiloxane of 1 weight part, and the content of solvent is the 35-45 weight part, and the content of mineral filler is the 8-12 weight part.
3. battery diaphragm composition according to claim 1 is characterized in that, described solvent is selected from a kind of in acetone, tetrahydrofuran (THF), the toluene.
4. battery diaphragm composition according to claim 1 is characterized in that, the median size of described mineral filler is 100-1000nm.
5. according to claim 1 or 4 described battery diaphragm compositions, it is characterized in that described mineral filler is selected from one or more in calcium oxide, magnesium oxide, aluminum oxide, zirconium white, zinc oxide, titanium oxide, kaolin, asbestos, Magnesium Silicate q-agent, Calucium Silicate powder, pure aluminium silicate, lime carbonate, barium sulfate and the barium titanate.
6. battery diaphragm, described battery diaphragm by at porous polyolefin membrane coating on both sides barrier film with composition and solidify and obtain, it is characterized in that described barrier film composition is the described battery diaphragm composition of claim 1.
7. battery diaphragm according to claim 6 is characterized in that, described battery diaphragm is 1-50g/cm with the consumption of composition
2
8. battery diaphragm according to claim 6 is characterized in that, the aperture of described porous polyolefin membrane is 50-300nm, and porosity is 15-50%, and thickness is 10-40 μ m.
9. battery diaphragm according to claim 6 is characterized in that, the described ultraviolet light polymerization that is cured as, and condition of cure comprises: solidification value is 20-60 ℃, be 5-30min set time.
10. lithium-ion secondary cell, this battery comprises battery container, electrode group and electrolytic solution, electrode group and electrolytic solution are sealed in the battery container, the electrode group comprises reels or stacked positive plate, barrier film and negative plate successively, it is characterized in that described barrier film is the described battery diaphragm of claim 6.
11. lithium-ion secondary cell according to claim 10, wherein, described battery diaphragm is attached on described positive plate and/or the negative plate two sides.
12. lithium-ion secondary cell according to claim 10, wherein, the thickness of described battery diaphragm is the 15-60 micron.
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|---|---|---|---|
| CN201010139327A CN102206420B (en) | 2010-03-30 | 2010-03-30 | Composition for battery diaphragm, battery diaphragm and lithium-ion secondary battery |
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|---|---|---|---|
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103421190A (en) * | 2013-07-23 | 2013-12-04 | 中南大学 | Comb polysilicone and solid electrolyte, preparation method and application thereof |
| CN103441229A (en) * | 2013-07-23 | 2013-12-11 | 清华大学 | Battery separator and preparation method thereof |
| WO2014183656A1 (en) * | 2013-05-15 | 2014-11-20 | Shenzhen Byd Auto R&D Company Limited | Separator and method for preparing the same |
| CN104124416B (en) * | 2014-05-22 | 2016-11-30 | 江苏华东锂电技术研究院有限公司 | Polyolefin composite diaphragm and preparation method thereof, and lithium ion battery |
| CN109686904A (en) * | 2019-03-19 | 2019-04-26 | 上海恩捷新材料科技有限公司 | Cell coating film slurry, battery diaphragm, secondary cell and preparation method thereof |
| CN110120484A (en) * | 2013-10-18 | 2019-08-13 | 米尔泰克紫光国际有限公司 | Polymer bonding ceramic particle battery separator coating |
| CN112310558A (en) * | 2020-10-30 | 2021-02-02 | 合肥国轩高科动力能源有限公司 | Inorganic coating slurry coated on diaphragm, manufacturing method and inorganic coating diaphragm |
| CN115275525A (en) * | 2022-08-23 | 2022-11-01 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttling effect, preparation process thereof and lithium-sulfur battery using diaphragm |
| WO2023065178A1 (en) * | 2021-10-20 | 2023-04-27 | 宁德时代新能源科技股份有限公司 | Electrode assembly, battery, battery module, battery pack, and electronic apparatus |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014183656A1 (en) * | 2013-05-15 | 2014-11-20 | Shenzhen Byd Auto R&D Company Limited | Separator and method for preparing the same |
| CN103441229A (en) * | 2013-07-23 | 2013-12-11 | 清华大学 | Battery separator and preparation method thereof |
| CN103441229B (en) * | 2013-07-23 | 2015-06-24 | 清华大学 | Battery separator and preparation method thereof |
| CN103421190B (en) * | 2013-07-23 | 2016-03-30 | 中南大学 | A kind of comb shape polysiloxane and solid electrolyte, preparation method and application |
| CN103421190A (en) * | 2013-07-23 | 2013-12-04 | 中南大学 | Comb polysilicone and solid electrolyte, preparation method and application thereof |
| CN110120484A (en) * | 2013-10-18 | 2019-08-13 | 米尔泰克紫光国际有限公司 | Polymer bonding ceramic particle battery separator coating |
| CN104124416B (en) * | 2014-05-22 | 2016-11-30 | 江苏华东锂电技术研究院有限公司 | Polyolefin composite diaphragm and preparation method thereof, and lithium ion battery |
| CN109686904A (en) * | 2019-03-19 | 2019-04-26 | 上海恩捷新材料科技有限公司 | Cell coating film slurry, battery diaphragm, secondary cell and preparation method thereof |
| CN112310558A (en) * | 2020-10-30 | 2021-02-02 | 合肥国轩高科动力能源有限公司 | Inorganic coating slurry coated on diaphragm, manufacturing method and inorganic coating diaphragm |
| WO2023065178A1 (en) * | 2021-10-20 | 2023-04-27 | 宁德时代新能源科技股份有限公司 | Electrode assembly, battery, battery module, battery pack, and electronic apparatus |
| JP7567101B2 (en) | 2021-10-20 | 2024-10-16 | 香港時代新能源科技有限公司 | Electrode assembly, battery, battery module, battery pack and power consuming device |
| CN115275525A (en) * | 2022-08-23 | 2022-11-01 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttling effect, preparation process thereof and lithium-sulfur battery using diaphragm |
| CN115275525B (en) * | 2022-08-23 | 2023-08-22 | 吉林师范大学 | Diaphragm for inhibiting polysulfide shuttle effect, preparation process thereof and lithium sulfur battery using diaphragm |
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| Publication number | Publication date |
|---|---|
| CN102206420B (en) | 2012-10-17 |
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