CN114388983A - Composite diaphragm and preparation method thereof, secondary battery and preparation method - Google Patents

Composite diaphragm and preparation method thereof, secondary battery and preparation method Download PDF

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Publication number
CN114388983A
CN114388983A CN202210016849.2A CN202210016849A CN114388983A CN 114388983 A CN114388983 A CN 114388983A CN 202210016849 A CN202210016849 A CN 202210016849A CN 114388983 A CN114388983 A CN 114388983A
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China
Prior art keywords
coating
electrolyte
base film
secondary battery
composite
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Pending
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CN202210016849.2A
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Chinese (zh)
Inventor
曹礼
周玲
李雄成
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Hunan Lifang New Energy Science and Technology Co Ltd
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Hunan Lifang New Energy Science and Technology Co Ltd
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Priority to CN202210016849.2A priority Critical patent/CN114388983A/en
Publication of CN114388983A publication Critical patent/CN114388983A/en
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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
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H01M50/457—Separators, membranes or diaphragms characterised by the material having a layered structure comprising three or more layers
    • 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
    • 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
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • 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 belongs to the technical field of secondary batteries, and particularly relates to a composite diaphragm and a preparation method thereof, a lithium ion battery and a preparation method thereof. According to the composite diaphragm provided by the invention, the coating layer containing the electrolyte is arranged, and after a bare cell and a shell are packaged, baked and vacuum-packaged during battery preparation, heating and pressurizing are carried out, so that the electrolyte in the coating layer is released from a capsule material, and the electrolyte infiltrates a pole piece and the diaphragm, so that the processes of liquid injection and standing are omitted, and the production efficiency is greatly improved.

Description

Composite diaphragm and preparation method thereof, secondary battery and preparation method
Technical Field
The invention belongs to the technical field of secondary batteries, and particularly relates to a composite diaphragm and a preparation method thereof, a secondary battery and a preparation method thereof.
Background
At present lithium electricity trade electric core is by positive negative pole piece, naked electric core is constituteed together to the diaphragm, the diaphragm main action is for being used for insulating, avoid switching on the short circuit between the positive negative pole, naked electric core is put into the aluminium and is moulded the shell and encapsulate, the encapsulation back vacuum is toasted and is got rid of unnecessary moisture, then annotate liquid to electric core, annotate the liquid back electric core and stew, ensure that pole piece/diaphragm are all infiltrated by electrolyte, electrolyte is as positive negative pole ion motion's carrier, as indispensable a material, annotate liquid back electric core and become to charge, make electric core electrified, detach the inside gaseous secondary encapsulation of accomplishing of electric core again, electric core accomplishes. The liquid injection and the standing after the liquid injection are needed, the treatment time is longer, and the production time is greatly increased.
Disclosure of Invention
One of the objects of the present invention is: aiming at the defects of the prior art, the composite diaphragm is provided with the coating layer containing the electrolyte, so that the time for injecting the electrolyte and the standing time can be saved during the preparation of the battery, and the production efficiency is greatly improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
the utility model provides a composite diaphragm, includes the base film, coats in at least one surperficial coating layer and the insulating layer of base film, and the insulating layer coats in the coating layer and keeps away from a base film surface, the coating layer includes bag material and electrolyte, bag material parcel electrolyte.
The composite diaphragm comprises a base film, a coating layer and an insulating layer, wherein the base film bears the coating layer with electrolyte, and the insulating layer is arranged on the surface of the coating layer, so that the insulating effect is achieved. When the composite diaphragm is assembled into a battery, the electric core arranged on the shell is heated and pressurized, so that the capsule material wrapping the electrolyte in the coating layer is broken, and the electrolyte flows out to infiltrate the pole piece, so that the secondary battery is prepared by subsequent formation.
Preferably, the thickness of the coating layer is 10-50 μm. The thickness of the coating layer is 10 μm, 12 μm, 16 μm, 24 μm, 28 μm, 32 μm, 35 μm, 40 μm, 42 μm, 46 μm, 48 μm, 50 μm.
Preferably, the thickness of the insulating layer is 1-10 μm. The thickness of the insulating layer was 1 μm, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, and 10 μm.
Preferably, the thickness of the base film is 3 to 60 μm. The thickness of the base film was 3 μm, 6 μm, 9 μm, 15 μm, 19 μm, 21 μm, 26 μm, 28 μm, 34 μm, 39 μm, 43 μm, 48 μm, 53 μm, 56 μm, 57 μm, 58 μm, 59 μm, 60 μm.
The second purpose of the invention is: aiming at the defects of the prior art, the preparation method of the composite diaphragm is simple, good in controllability and capable of realizing batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a composite diaphragm comprises the following steps:
s1, selecting electrolyte and a capsule material, mixing the electrolyte and the capsule material to form a core-shell structure, coagulating and precipitating, and curing to obtain coating slurry;
s2, selecting a base film, coating the coating slurry on at least one surface of the base film, and drying to form a coating layer to obtain a pretreatment film;
and S3, selecting insulating slurry, coating the insulating slurry on the surface of the coating layer, and drying to form the insulating layer to obtain the composite diaphragm.
According to the preparation method of the composite diaphragm, the electrolyte is used as a capsule core and is mixed with a capsule material to form a core-shell structure, reaction is carried out to obtain coating slurry, the coating slurry is coated on the surface of a base film and dried to obtain a coating layer, and the insulating slurry is coated on the surface of the coating layer and dried to obtain an insulating layer, so that the composite diaphragm is obtained.
Preferably, the capsule wall material comprises one or a mixture of polyamide, polyacrylic resin and polypropylene. Depending on the selection of the capsule wall material, different precipitation methods can be selected, and the phase separation method can be classified into a single-aggregation method, a complex-aggregation method, a solvent-non-solvent method, a drying method in a liquid, and the like.
The third purpose of the invention is that: in order to overcome the defects of the prior art, the secondary battery has high capacity retention rate and good safety.
In order to achieve the purpose, the invention adopts the following technical scheme:
a secondary battery comprises the composite diaphragm. The secondary battery comprises a positive plate, a diaphragm, a negative plate and a shell, wherein the positive plate and the negative plate are separated by the diaphragm, the positive plate, the diaphragm and the negative plate are arranged on the shell, and the diaphragm is the composite diaphragm. The secondary battery may be a lithium ion battery, a sodium ion battery, a magnesium ion battery, or the like, and preferably, the secondary battery is a lithium ion battery. The following description is set forth in terms of a lithium ion battery.
Wherein, the positive plate comprises a positive current collector and a positive active material arranged on at least one surface of the positive current collector, and the positive active material layer can be of a chemical formula including but not limited to LiaNixCoyMzO2-bNb(wherein a is more than or equal to 0.95 and less than or equal to 1.2, x>0, y is more than or equal to 0, z is more than or equal to 0, and x + y + z is 1,0 is more than or equal to b and less than or equal to 1, M is selected from one or more of Mn and Al, N is selected from one or more of F, P and S), and the positive electrode active material can also be selected from one or more of LiCoO (lithium LiCoO), but not limited to2、LiNiO2、LiVO2、LiCrO2、LiMn2O4、LiCoMnO4、Li2NiMn3O8、LiNi0.5Mn1.5O4、LiCoPO4、LiMnPO4、LiFePO4、LiNiPO4、LiCoFSO4、CuS2、FeS2、MoS2、NiS、TiS2And the like. The positive electrode active material may be further modified, and the method of modifying the positive electrode active material is known to those skilled in the art, for example, the positive electrode active material may be modified by coating, doping, and the like, and the material used in the modification may be one or a combination of more of Al, B, P, Zr, Si, Ti, Ge, Sn, Mg, Ce, W, and the like. While the positive current collector is generally a structure or part that collects current, the positive current collector may be any suitable structure or part in the artFor example, the positive electrode current collector may include, but is not limited to, a metal foil, and more specifically, may include, but is not limited to, an aluminum foil.
The negative plate comprises a negative current collector and a negative active substance arranged on at least one surface of the negative current collector, wherein the negative active substance can include one or more of graphite, soft carbon, hard carbon, carbon fiber, mesocarbon microbeads, silicon-based materials, tin-based materials, lithium titanate or other metals capable of forming an alloy with lithium. Wherein, the graphite can be selected from one or more of artificial graphite, natural graphite and modified graphite; the silicon-based material can be one or more selected from simple substance silicon, silicon-oxygen compound, silicon-carbon compound and silicon alloy; the tin-based material can be one or more selected from simple substance tin, tin oxide compound and tin alloy. The negative electrode current collector is generally a structure or a part for collecting current, and the negative electrode current collector may be any material suitable for use as a negative electrode current collector of a lithium ion battery in the art, for example, the negative electrode current collector may include, but is not limited to, a metal foil, and the like, and more specifically, may include, but is not limited to, a copper foil, and the like.
The lithium ion battery also comprises electrolyte, and the electrolyte comprises an organic solvent, electrolyte lithium salt and an additive. Wherein the electrolyte lithium salt may be LiPF used in a high-temperature electrolyte6And/or LiBOB; or LiBF used in low-temperature electrolyte4、LiBOB、LiPF6At least one of; or LiBF used in anti-overcharge electrolyte4、LiBOB、LiPF6At least one of, LiTFSI; may also be LiClO4、LiAsF6、LiCF3SO3、LiN(CF3SO2)2At least one of (1). And the organic solvent may be a cyclic carbonate including PC, EC; or chain carbonates including DFC, DMC, or EMC; and also carboxylic acid esters including MF, MA, EA, MP, etc. And additives including, but not limited to, film forming additives, conductive additives, flame retardant additives, anti-overcharge additives, additives to control the H2O and HF content of the electrolyte, additives to improve low temperature performanceAt least one of additives and multifunctional additives.
The housing is made of any one of aluminum plastic film and stainless steel, and preferably, the housing is made of aluminum plastic film.
The fourth purpose of the invention is that: aiming at the defects of the prior art, the preparation method of the secondary battery is provided, has simple operation and good controllability, and can be used for batch production.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for manufacturing a secondary battery, comprising the steps of:
a1, selecting a positive plate and a negative plate, and sequentially placing the positive plate, the composite diaphragm and the negative plate to prepare a bare cell;
and A2, selecting a shell, placing the bare cell in the shell for packaging, baking, vacuum packaging, heating and pressurizing, forming, degassing and secondary packaging to obtain the secondary battery.
The preparation of the secondary battery adopts the composite diaphragm with the coating layer, the coating layer contains the wrapped electrolyte, the positive plate, the composite diaphragm and the negative plate are assembled into the bare cell, and then the secondary battery is prepared by packaging, baking, vacuum packaging, heating and pressurizing, formation, degassing and secondary packaging, so that the standing time after liquid injection and liquid injection can be saved, and the production efficiency is greatly improved.
Preferably, in the step A2, the heating temperature is 45-60 ℃, the pressurizing pressure is 0.1-0.2 mpa/pc, and the pressurizing time is 5-10 min. Certain temperature and pressure are set, so that the capsule material in the coating layer can be broken to release electrolyte, the temperature and the pressure are too high, the battery core is easily damaged, the temperature and the pressure are too low, the capsule material is not broken completely, and part of the electrolyte is not released, so that the electrolyte cannot completely soak the pole piece, and the phenomenon of lithium precipitation or black spot precipitation is easily caused. The pressure borne by each battery cell is 0.1-0.2 mpa, and the required pressure can be correspondingly calculated if a plurality of battery cells are placed at one time according to the use condition.
Preferably, the baking temperature in the step A2 is 80-90 ℃. Set up certain stoving temperature, detach the moisture in naked electric core and the casing, avoid follow-up electrolyte and moisture reaction, influence battery performance.
Compared with the prior art, the invention has the beneficial effects that: according to the composite diaphragm, the coating layer containing the electrolyte is arranged, and when the battery is prepared, the bare cell and the shell are packaged, baked and vacuum-packaged, and then heated and pressurized, so that the electrolyte in the coating layer is released from the capsule material, the pole piece and the diaphragm are soaked by the electrolyte, the processes of liquid injection and standing are omitted, 24-72 hours are saved, and the production efficiency is greatly improved.
Drawings
FIG. 1 is a schematic diagram of the present invention.
FIG. 2 is a second schematic structural diagram of the present invention.
Wherein: 1. a base film; 2. a coating layer; 3. an insulating layer.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and the accompanying drawings, but the embodiments of the invention are not limited thereto.
Example 1
1. The utility model provides a composite membrane, includes base film 1, coat 2 and insulating layer 3, coats in the both sides surface of base film 1 with coat 2, and insulating layer 3 coats in one surface that base film 1 was kept away from to coat 2. Wherein the thickness of the base film 1 is 15 μm, the thickness of the coating layer 2 is 25 μm, and the thickness of the insulating layer 3 is 8 μm.
2. A preparation method of a composite diaphragm comprises the steps of mixing polyacrylic resin serving as a capsule wall material with an electrolyte floating liquid, controlling conditions to enable the capsule wall material to be condensed and deposited around a capsule core object to form capsules, curing the capsule wall material to obtain coating slurry, coating the coating slurry on the surfaces of two sides of a base membrane 1, and drying to form a coating layer 2 to obtain a pretreatment membrane; mixing ceramic powder and PVDF binder to prepare insulating slurry, coating the insulating slurry on the surface of the coating layer 2, and drying to form an insulating layer 3 to obtain the composite diaphragm, as shown in FIG. 2.
3. The utility model provides a lithium ion battery, includes positive plate, diaphragm, negative pole piece and casing, positive plate and negative pole piece are separated to the diaphragm, and positive plate, diaphragm and negative pole piece are installed to the casing, the diaphragm is foretell composite diaphragm.
4. A preparation method of a lithium ion battery comprises the following steps:
a1, selecting an aluminum foil as a positive plate and a copper foil as a negative plate, and sequentially placing the positive plate, the composite diaphragm and the negative plate to prepare a bare cell;
and A2, selecting an aluminum plastic film as a shell, placing the bare cell in the shell for packaging, placing the bare cell in the shell for vacuum baking at 85 ℃, vacuum packaging, heating to 50 ℃, applying 0.2mpa pressure for 8min to crush the cell in the coating layer 2, forming, removing redundant gas in the coating layer, and performing secondary packaging to obtain the lithium ion battery.
Example 2
The difference from example 1 is that: mixing polyacrylic resin serving as a capsule wall material with an electrolyte floating liquid, controlling conditions to enable the capsule wall material to be condensed and deposited around a capsule core object to form capsules, curing the capsule wall material to obtain coating slurry, coating the coating slurry on one side surface of a base membrane 1, and drying to form a coating layer 2 to obtain a pretreatment membrane; mixing ceramic powder and PVDF binder to prepare insulating slurry, coating the insulating slurry on the surface of the coating layer 2, and drying to form an insulating layer 3 to obtain the composite diaphragm, as shown in figure 1.
The rest is the same as embodiment 1, and the rest is not described again.
Example 3
The difference from example 1 is that: in the step A2, the heating temperature is 48 ℃, the pressure is 0.1mpa, and the pressurizing time is 6 min.
The rest is the same as embodiment 1, and the rest is not described again.
Example 4
The difference from example 1 is that: in the step A2, the heating temperature is 50 ℃, the pressure is 0.1mpa, and the pressurizing time is 8 min.
The rest is the same as embodiment 1, and the rest is not described again.
Example 5
The difference from example 1 is that: in the step A2, the heating temperature is 53 ℃, the pressure is 0.1mpa, and the pressurizing time is 5 min.
The rest is the same as embodiment 1, and the rest is not described again.
Example 6
The difference from example 1 is that: in the step A2, the heating temperature is 58 ℃, the pressure is 0.1mpa, and the pressurizing time is 7 min.
The rest is the same as embodiment 1, and the rest is not described again.
Example 7
The difference from example 1 is that: in the step A2, the heating temperature is 60 ℃, the pressure is 0.1mpa, and the pressurizing time is 6 min.
The rest is the same as embodiment 1, and the rest is not described again.
Example 8
The difference from example 1 is that: in the step A2, the heating temperature is 54 ℃, the pressure is 0.1mpa, and the pressurizing time is 7 min.
The rest is the same as embodiment 1, and the rest is not described again.
Comparative example 1
The difference from example 1 is that: mixing ceramic powder and PVDF binder to prepare insulating slurry, coating the insulating slurry on the surface of the coating layer 2, drying to form an insulating layer 3 to obtain a composite diaphragm, selecting an aluminum foil as a positive plate and a copper foil as a negative plate, and sequentially placing the positive plate, the composite diaphragm and the negative plate to prepare a bare cell.
The rest is the same as embodiment 1, and the rest is not described again.
Comparative example 2
The difference from example 1 is that: the preparation method of the diaphragm comprises the steps of mixing ceramic powder and a PVDF binder to prepare insulating slurry, coating the insulating slurry on the surface of a coating layer 2, drying to form an insulating layer 3 to obtain a composite diaphragm, selecting an aluminum-plastic film as a shell, placing a bare cell in the shell, injecting electrolyte to the shell for packaging, placing the shell at 85 ℃, baking in vacuum, packaging in vacuum, heating to 50 ℃, applying 0.2mpa pressure for 8min to crush the cell in the coating layer 2, forming, removing redundant gas in the cell, and packaging for the second time to obtain the lithium ion battery.
The rest is the same as embodiment 1, and the rest is not described again.
And (3) performance testing: the lithium ion batteries prepared in the above examples 1 to 8 and comparative examples 1 to 2 were subjected to a capacity retention ratio test and a production time test for 300 charge-discharge cycles, and the test results are reported in table 1.
TABLE 1
Figure BDA0003460002920000081
As can be seen from table 1, the prepared lithium ion battery of the present invention has better capacity retention rate and shorter production time compared to the prior art lithium ion battery. From comparison of examples 1 to 8, when the heating temperature is set at 50 ℃ and 0.2mpa pressure is applied for 8min, the prepared lithium ion battery can produce a lithium ion battery with higher capacity retention rate in shorter production time. Compared with the comparative example 1, the composite diaphragm prepared by the invention still has good capacity retention rate, shorter production time and high production efficiency. Compared with the conventional lithium ion battery, the lithium ion battery prepared by using the composite diaphragm prepared by the invention has shorter production time because the conventional production time needs to be injected with liquid and needs to be kept stand after the injection, the production time is increased, and the production efficiency is reduced, while the composite diaphragm is formed by coating the electrolyte prepared by preparing the verification structure on the surface of the base film 1, the injection time is saved, the electrolyte is extracted from the capsule material when heating and pressurizing are carried out, so that the pole piece is soaked by the electrolyte under the heating and pressurizing conditions, and the production time is reduced.
Variations and modifications to the above-described embodiments may also occur to those skilled in the art, which fall within the scope of the invention as disclosed and taught herein. Therefore, the present invention is not limited to the above-mentioned embodiments, and any obvious improvement, replacement or modification made by those skilled in the art based on the present invention is within the protection scope of the present invention. Furthermore, although specific terms are employed herein, they are used in a generic and descriptive sense only and not for purposes of limitation.

Claims (10)

1. The utility model provides a composite diaphragm which characterized in that, includes the base film, coats in the coating and the insulating layer of at least one surface of base film, and the insulating layer coats and keeps away from a base film surface in the coating, the coating includes bag material and electrolyte, bag material parcel electrolyte.
2. The composite separator according to claim 1, wherein the thickness of the coating layer is 10 to 50 μm.
3. The composite separator according to claim 1 or 2, wherein the thickness of the insulating layer is 1 to 10 μm.
4. The composite separator according to claim 3, wherein the thickness of the base film is 3 to 60 μm.
5. Method for the production of a composite membrane according to any one of claims 1 to 4, characterized in that it comprises the following steps:
s1, selecting electrolyte and a capsule material, mixing the electrolyte and the capsule material to form a core-shell structure, coagulating and precipitating, and curing to obtain coating slurry;
s2, selecting a base film, coating the coating slurry on at least one surface of the base film, and drying to form a coating layer to obtain a pretreatment film;
and S3, selecting insulating slurry, coating the insulating slurry on the surface of the coating layer, and drying to form the insulating layer to obtain the composite diaphragm.
6. The preparation method of the composite membrane as claimed in claim 5, wherein the capsule wall material comprises one or more of polyamide, polyacrylic resin and polypropylene.
7. A secondary battery comprising the composite separator as defined in any one of claims 1 to 4.
8. The method for manufacturing a secondary battery according to claim 7, comprising the steps of:
a1, selecting a positive plate and a negative plate, and sequentially placing the positive plate, the composite diaphragm and the negative plate to prepare a bare cell;
and A2, selecting a shell, placing the bare cell in the shell for packaging, baking, vacuum packaging, heating and pressurizing, forming, degassing and secondary packaging to obtain the secondary battery.
9. The method for manufacturing a secondary battery according to claim 8, wherein the heating temperature in the step A2 is 45-60 ℃, the pressurizing pressure is 0.1-0.2 mpa/pc, and the pressurizing time is 5-10 min.
10. The method for manufacturing a secondary battery according to claim 8 or 9, wherein the baking temperature in the step a2 is 80 to 90 ℃.
CN202210016849.2A 2022-01-07 2022-01-07 Composite diaphragm and preparation method thereof, secondary battery and preparation method Pending CN114388983A (en)

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CN112366351A (en) * 2020-10-16 2021-02-12 山东海科创新研究院有限公司 Lithium-supplementing slow-release capsule, electrolyte thereof and lithium ion battery
CN113410517A (en) * 2021-06-04 2021-09-17 珠海冠宇电池股份有限公司 Slow-release electrolyte, preparation thereof and application thereof in lithium ion battery
KR20210132303A (en) * 2020-04-27 2021-11-04 에스케이이노베이션 주식회사 Lithium Secondary Battery

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10151830A1 (en) * 2001-10-20 2003-04-30 Dilo Trading Ag Zug Lithium secondary battery, especially lithium-polymer stacked or wound battery, contains microcapsules with suitable contents in cathode and/or anode composition and/or separator
US20130316221A1 (en) * 2011-12-27 2013-11-28 Lg Chem, Ltd. Lithium secondary battery and preparation thereof
CN104011925A (en) * 2011-12-27 2014-08-27 株式会社Lg化学 Lithium secondary battery and method for producing same
US20150050543A1 (en) * 2013-08-17 2015-02-19 Robert Bosch Gmbh Li/Metal Battery with Microstructured Solid Electrolyte
US20150093635A1 (en) * 2013-10-01 2015-04-02 Robert Bosch Gmbh Additive for an electrolyte of a lithium-based secondary battery cell
CN106384802A (en) * 2016-11-08 2017-02-08 曙鹏科技（深圳）有限公司 Battery diaphragm and preparation method thereof as well as lithium ion battery
CN109585783A (en) * 2018-12-03 2019-04-05 桑顿新能源科技有限公司 A kind of wetting method of lithium ion battery and its pole piece
KR20210132303A (en) * 2020-04-27 2021-11-04 에스케이이노베이션 주식회사 Lithium Secondary Battery
CN112366351A (en) * 2020-10-16 2021-02-12 山东海科创新研究院有限公司 Lithium-supplementing slow-release capsule, electrolyte thereof and lithium ion battery
CN113410517A (en) * 2021-06-04 2021-09-17 珠海冠宇电池股份有限公司 Slow-release electrolyte, preparation thereof and application thereof in lithium ion battery

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