CN101393975A - Colloidal state polymer battery and composite diaphragm manufacturing method therefor - Google Patents
Colloidal state polymer battery and composite diaphragm manufacturing method therefor Download PDFInfo
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- CN101393975A CN101393975A CNA2008102168228A CN200810216822A CN101393975A CN 101393975 A CN101393975 A CN 101393975A CN A2008102168228 A CNA2008102168228 A CN A2008102168228A CN 200810216822 A CN200810216822 A CN 200810216822A CN 101393975 A CN101393975 A CN 101393975A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to a method for preparing a colloidal state polymer battery and a composite membrane thereof. During the preparation of the composite membrane, firstly a high molecular polymer is dissolved in a solution to form a polymer solution; then the membrane is dipped into the polymer solution and a phase separating agent respectively; and finally the composite membrane with two surfaces coated with high-porosity high molecular polymer layers is obtained after the baking operation is carried out. Compared with the prior art, the method for preparing the colloidal state polymer battery and the composite membrane thereof has the following advantages: the membrane is dipped into the polymer solution and the phase separating agent sequentially, and a mixed solution of normal heptane and ethanol is taken as the phase separating agent, so that the finally prepared composite membrane has higher porosity, the characteristic of facilitating ion transmission is stronger, and the finally prepared colloidal state polymer battery has good performance such as higher specific energy, longer cycle life and lower internal drop within a wider temperature range.
Description
Technical field
The present invention relates to a kind of preparation method of battery, relate in particular to the preparation method of a kind of colloidal state polymer battery and composite diaphragm thereof.
Background technology
Since first commercialization lithium ion battery of Sony in 1991 comes out, the technology of people aspect high energy lithium ion cell constantly develops and innovates, lithium ion battery the most promising a new generation of 21 century " environmental type " battery of being known as.Along with Progress in technique, the particularly lasting fast development of the universal and portable type electronic product of mobile communication product, proposed an urgent demand to the miniature charging battery more reliable performance, in order to satisfy this demand, lithium ion battery also must be done further to improve on battery structure and performance.Lithium ion battery generally is divided into liquid lithium ionic cell (LIB) and solid lithium ion battery (generally is called polymer Li-ion battery, PLIB).The leakage that outstanding problem be exactly electrolyte solution of liquid lithium ionic cell in application includes inflammable component in the battery, as organic electrolyte solution and lithium carbide, can cause fire behind the electrolyte leakage.If replace liquid electrolyte with polymer then can avoid electrolytical leakage.But the ionic conductivity of polymer dielectric is lower than the electrolytical conductivity of liquid phase.The gel polymer electrolyte of being made up of polymeric matrix, solvent or plasticizer substitutes all solid state polymer dielectric and just can improve ionic conductivity.Therefore, just having the end of the nineties with gel polymer electrolyte is that electrolytical polymer Li-ion battery puts goods on the market.The operation principle of polymer Li-ion battery is identical with liquid lithium ionic cell, and the electrolyte of different is polymer Li-ion battery is that liquid organic bath is adsorbed on a kind of polymer substrate.The present liquid lithium ionic cell capacity of polymer Li-ion battery Capacity Ratio is big, and because the polymer battery material softness, and the battery no leakage is easy to make the battery of ultrathin and arbitrary shape.But such colloidal state polymer battery processing procedure complexity, technology cost height, the mechanical strength of polymer electrolyte diaphragm is bad simultaneously, and temperature coefficient is very big, at room temperature the colloidal state polymer electrolyte still can play the effect of electronic isolation, and the both positive and negative polarity of electric core is separated.But when temperature raises or battery is when being subjected to certain external pressure, this type of polymer dielectric will soften rapidly, its mechanical performance variation so that can't keep original barrier film shape and thickness, promptly can't continue the both positive and negative polarity in the electric core is separated.Therefore, the both positive and negative polarity at some position can be interconnected to form short circuit in the electric core, causes taking place safety issue.
Also have polymer battery to adopt composite diaphragm at present, it is dissolved in solvent with high molecular polymer glue earlier, and this solvent comprises the composition that can dissolve described high molecular polymer glue, and the barrier film with TPO is immersed in the described solvent then, dries at last.Originally do not have in the prior art can deposit glue in the micropore of the polymer film before the gluing yet, and can cause original hole part to stop up, glue be the two sides that is coated in original polymer film fully, thereby influences the porosity and the air penetrability of original polymer film.
Summary of the invention
One of technical problem to be solved by this invention provides a kind of preparation method of composite diaphragm, and the composite diaphragm of its preparation has higher porosity.
Be the preparation method's that solves above-mentioned composite diaphragm technical problem, the present invention adopts following technical scheme:
The preparation method of composite diaphragm comprises the steps:
S1, preparation polymer solution: high molecular polymer is dissolved in the solvent;
S2, coating: evenly apply above-mentioned polymer solution on the barrier film two sides, and form high polymer layer on the barrier film two sides;
Wherein, coating specifically comprises the steps: described in the step S2
S21, barrier film is immersed in the polymer solution;
S22, the barrier film after will soaking are immersed in the phase separation agent again;
S23, barrier film is dried promptly get composite diaphragm at last.
Two of technical problem to be solved by this invention is corresponding preparation methods that a kind of colloidal state polymer battery is provided, the colloidal state polymer battery of its preparation, and performance is better.
Be the preparation method's that solves above-mentioned colloidal state polymer battery technical problem, the present invention adopts following technical scheme:
The preparation method of colloidal state polymer battery comprises the steps:
Adopt the prepared composite diaphragm that comes out of the preparation method of technical solution of the present invention composite diaphragm, it is by the colloidal state polymer battery that the preparation method of the colloidal state polymer battery of technical solution of the present invention prepares, and the beneficial effect that is compared with the prior art is:
Owing to be taken up in order of priority and be immersed in polymer solvent and the phase separation agent, and adopt mixed solvent as phase separation agent, finally prepd composite diaphragm has higher porosity, thereby it promotes that the characteristic of ion transfer is stronger, make the final colloidal state polymer thing battery of making in wider temperature range, have more high-energy-density, more long circulation life and and superperformance such as lower internal drop.
Description of drawings
Fig. 1 is the discharge curve under the colloidal state polymer battery different multiplying in the specific embodiment of the invention one;
Fig. 2 is the cycle performance figure of colloidal state polymer battery in the specific embodiment of the invention one;
Fig. 3 is the discharge curve under the colloidal state polymer battery different multiplying in the specific embodiment of the invention two;
Fig. 4 is the cycle performance figure of colloidal state polymer battery in the specific embodiment of the invention two.
Embodiment
Example one
The colloidal state polymer battery preparation method of this embodiment comprises the steps:
One, the preparation of composite diaphragm
1, earlier high molecular polymer is dissolved in the solvent, forms macromolecule polymer solution.
Macromolecule polymer solution contains the high molecular polymer of 10-20% mass percent.Described high molecular polymer can be made up of in polymethyl methacrylate, polyacrylonitrile, Kynoar, Kynoar-hexafluoropropylene copolymer, poly(ethylene oxide), the polyvinyl acetate one or more.
In the technical scheme of the present invention, solvent is by propene carbonate, cyclohexanone, acetone, butanone, N-methyl pyrrolidone, N, dinethylformamide, N, one or more compositions in N-dimethylacetylamide and the dibutyl phthalate.
Being specially in this embodiment, is that Polyvinylidene and the polymethyl methacrylate of 1:1 is dissolved in N-methyl pyrrolidone and the N that the 1000g mass ratio is 3:1 with the 50g mass ratio, in the dinethylformamide mixed solution, promptly forms polymer solution.
2, evenly apply above-mentioned polymer solution again on the barrier film two sides and form the porous polymer polymeric layer
Described barrier film mainly is meant polyolefine isolating film used in the lithium ion battery, is made up of in polyethylene (PE), the polypropylene (PP) one or both.Barrier film can be an individual layer, also can be double-deck, in addition three layers and more than.
Described coating is meant: earlier barrier film is immersed in the polymer solution, soak time is 30-120 second.Polyalkene diaphragm after will soaking then is immersed in the phase separation agent again, soaks 60-120 second.Described phase separation agent can be made up of normal heptane, ethanol, and its ratio of components (mass ratio) is 1:1～1:10.Also have polymer battery to adopt composite diaphragm at present, it is dissolved in solvent with high molecular polymer glue earlier, and this solvent comprises the composition that can dissolve described high molecular polymer glue, and the barrier film with TPO is immersed in the described solvent then, dries at last.Originally do not have in the prior art can deposit glue in the micropore of the polymer film before the gluing yet, and can cause original hole part to stop up, glue be the two sides that is coated in original polymer film fully, thereby influences the porosity and the air penetrability of original polymer film.
Preferred normal heptane, ethanol mixed solvent are as phase separation agent in this embodiment, this mixed solvent is non-solvent concerning high molecular polymer, when so barrier film is immersed in the phase separation agent, because high polymer layer and the normal heptane of membrane surface, ethanol mixed solvent is immiscible and contraction immediately, solvent in the high polymer layer and normal heptane, ethanol mixed solvent are dissolved each other, so the solvent in the high polymer layer is just flooded out by normal heptane, ethanol mixed solvent.
Barrier film oven dry after will handling through phase separation agent at last, drying time is 120-500 second, bake out temperature is 90-120 ℃, the composite diaphragm that obtains like this is the porosity height not only, and the high molecular polymer in the barrier film in original micropore is all flooded, form homogeneous, the high polymer layer of high porosity on the polyalkene diaphragm two sides.In this embodiment particularly be, with thickness is that 20 microns polyolefin PP/PE barrier film soaked after 1 minute under 80 ℃ of conditions baking 2 minutes in polymer solution, in normal heptane, ethanol mixed solvent, soaked 1 minute again, under 90 ℃ of conditions, toasted 5 minutes at last, promptly get composite diaphragm.The thickness of the high polymer layer that forms is generally the 10-30 micron, and porosity is the microcellular structure more than 75%.
Two, the making of polymer colloidal state battery
This embodiment is made the colloidal state polymer lithium ion battery on the basis of prolonging with the manufacture craft of traditional plastic-aluminum flexible-packed battery, mainly is the making of introducing electric core certainly herein.The colloidal polymeric lithium ion battery mainly is made up of positive plate, negative plate, barrier film and aluminium plastic composite packaging film four parts, therefore need be ready to positive plate and negative plate earlier, just can make electric core then, and barrier film then adopts the composite diaphragm of aforementioned preparation.
1, make positive plate:
The 1-5g Kynoar is dissolved in the N-methyl pyrrolidone, add the 6-12g conductive carbon black then, add 20-30g positive active material (positive active material is one or more in cobalt acid lithium, LiMn2O4, LiFePO 4, high-nickel material and the trielement composite material) at last, after high-speed stirred is even, make anode sizing agent.In the positive plate of this embodiment, cobalt acid lithium, conductive carbon black, binding agent Kynoar three's mass ratio is 93:4:3.Then aforementioned anode sizing agent is coated on thickness and is on two surfaces of aluminium foil of 16 microns, 130 ℃ dry down, to remove the N-methyl pyrrolidone that desolvates.Become the specification of 43mm * 308mm at last through cutting after the roll-in, on the initial aluminium foil surface of not filming, put the aluminium pole ears band of burn-oning then, promptly form positive plate.
2, make negative plate:
The 1-8g Kynoar is dissolved in the N-methyl pyrrolidone, adds the 3-8g conductive carbon black then, add 15-25g graphite at last, after high-speed stirred is even, make cathode size.In the negative plate of this embodiment, graphite, conductive carbon black, binding agent Kynoar three's mass ratio is 92:3:5.At last slurry is coated on two surfaces of 12 micron thickness Copper Foils, at 130 ℃ of dry down N-methyl pyrrolidones that desolvate that remove, pole piece becomes 44mm * 348mm specification through cutting after the roll-in, puts the nickel lug band of burn-oning then on the initial copper-clad surface of not filming, and promptly forms negative plate.
3, make electric core:
At first, positive and negative plate and the composite diaphragm that cuts are folded in proper order by positive plate-composite diaphragm-negative plate-composite diaphragm, be placed on the specification that is wound into 3.1mm * 32mm * 48mm on the up-coiler then.Then, it was toasted 10 hours under 90 ℃ of conditions of vacuum, reinstall in the plastic-aluminum combined film package bag of casing forming.Plastic-aluminum combined film package bag is carried out hot-pressing, edge-sealing, and the reservation liquid injection port forms electric core semi-finished product.At last, 2-5g is consisted of: LiPF
6(1mol/L)+electrolyte of EC-DEC-DMC (1:1:1) injects electric core by aforementioned liquid injection port, again with the liquid injection port hot-pressing, edge-sealing, and carries out curing reaction after leaving standstill 5-10h.The process conditions of curing reaction are: will pour into electrolyte earlier and heat a period of time through the electric core after sealing, heating-up temperature is 80-120 ℃, be 150-300 second heating time, then electric core natural cooling is solidified, between composite diaphragm, electrolyte and the pole piece curing reaction has taken place after solidifying, secure bond together between electric core positive and negative plate and the barrier film.
Adopt the composite diaphragm of prior art for preparing under very high temperature, could solidify.And the composite diaphragm that adopts technical solution of the present invention to prepare, it just can solidify under lower temperature.As everyone knows, curing temperature is high more, and is big more to the performance side effect of battery, therefore adopts the colloidal state polymer battery of technical solution of the present invention preparation, and its performance is better.The electrolyte that injects in this concrete real-time mode is 2.3g, and electric core leaves standstill 8h behind the liquid injection port hot-pressing, edge-sealing, and with electric core heating, curing temperature is 87 ± 5 ℃ again, and the time is 120s.Through test, the Specifeca tion speeification of the colloidal state polymer battery of producing is:
Capacity: 700mAh
End of charge voltage 4.2V
Final discharging voltage 3.0V
Multiplying power discharging curve and cycle performance figure (adopting 1C to charge and discharge) see Fig. 1 and Fig. 2.
In sum, the colloidal state polymer battery that adopts the present invention to make no longer contains the electrolyte of free state in the electric core, thereby the probability that battery leakage, corrosion harmfulness and blast occur goes to zero; Simultaneously owing between composite diaphragm, electrolyte and the pole piece curing reaction has taken place, secure bond makes electric core form one and has certain mechanical strength together between electric core positive and negative plate and the barrier film, and is solid, whole closely; In addition, because composite diaphragm plays except resembling the common batteries barrier film the effect of isolating both positive and negative polarity, owing to have higher porosity, thereby himself promotes the characteristic of ion transfer in addition, and common diaphragm and electrolyte are compatible hardly, ion transmits in barrier film substantially to be finished by diffusion, so battery has high-energy-density, superperformances such as long circulation life and low internal drop in wide temperature range.In addition, employing technical solution of the present invention production colloidal state polymer battery has technological process and production equipment is simple, and running cost is low, and process is easy to control, the rate of finished products advantages of higher.
Example two
This specifically is to make the colloidal state polymer battery preparation method of mode and embodiment one roughly the same, and difference is some technological parameter difference, and concrete steps are briefly described below:
1, the preparation of composite diaphragm
In this embodiment, be that Polyvinylidene-hexafluoropropylene and the polyvinyl acetate of 2:1 is dissolved in acetone and the N that the 1000g mass ratio is 3:1 with the 60g mass ratio, in the dinethylformamide mixed solution.The polyolefin PP/PE barrier film that with thickness is 20 microns again soaked in mixed solution 1 minute, polyolefin PP/PE barrier film after will soaking then is immersed in normal heptane, the ethanol mixed solvent 1 minute, polyolefin PP/PE barrier film is toasted under 90 ℃ of conditions promptly got polymer dielectric/polyolefin composite diaphragm that the two sides is evenly coating high molecular polymer in 5 minutes at last.
2, the making of polymer colloidal state battery
This embodiment is anodal with the LiMn2O4, and native graphite is a negative pole, adopts the composite diaphragm of above-mentioned preparation, makes electric core according to the method for embodiment one.Wherein the mass ratio of LiMn2O4, conductive carbon black, binding agent Kynoar is 92:4:4 in the positive plate.The mass ratio of graphite, conductive carbon black, binding agent Kynoar is 92:3:5 in the negative plate.
The electrolyte that injects in the electricity core is 2.8g, and electric core leaves standstill 8h behind the liquid injection port hot-pressing, edge-sealing, is cured reaction.The process conditions of curing reaction are: with electric core heating a period of time, heating-up temperature is 80-120 ℃ earlier, and be 150-300 second heating time, then electric core natural cooling solidified.
The battery Specifeca tion speeification that adopts the method to make is as follows:
Capacity: 550mAh
End of charge voltage 4.2V
Final discharging voltage 3.0V
Multiplying power discharging curve and cycle performance figure (adopting 1C to charge and discharge) see Fig. 3 and Fig. 4.
Above content be in conjunction with concrete preferred implementation to further describing that the present invention did, can not assert that concrete enforcement of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, can also make some simple deduction or replace, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1, the preparation method of composite diaphragm comprises the steps:
S1, preparation polymer solution: high molecular polymer is dissolved in the solvent;
S2, coating: evenly apply above-mentioned polymer solution on the barrier film two sides, and form high polymer layer on the barrier film two sides;
It is characterized in that coating described in the step S2 specifically comprises the steps:
S21, barrier film is immersed in the polymer solution;
S22, the barrier film after will soaking are immersed in the phase separation agent again;
S23, at last barrier film is dried.
2, the preparation method of composite diaphragm as claimed in claim 1 is characterized in that, described phase separation agent is normal heptane and ethanol mixed solvent.
3, the preparation method of composite diaphragm as claimed in claim 2 is characterized in that, the quality ratio of components of normal heptane and ethanol is 1:1～1:10 in the phase separation agent.
4, the preparation method of the composite diaphragm described in claim 1 or 2 is characterized in that, the thickness of described high polymer layer is the 10-30 micron, and has the porosity of 20-75%.
5, the preparation method of the composite diaphragm described in claim 1 or 2 is characterized in that, the soak time that described in the step S21 barrier film is immersed in the polymer solution is 30-120 second.
6, the preparation method of the composite diaphragm described in claim 1 or 2 is characterized in that, the barrier film after will soaking described in the step S22 is immersed in and soaks in the phase separation agent 60-120 second.
7, the preparation method of the composite diaphragm described in claim 1 or 2 is characterized in that, the drying time of drying described in the step S23 is 120-500 second, and bake out temperature is 90-120 ℃.
8, the preparation method of composite diaphragm as claimed in claim 1 or 2, it is characterized in that, solvent described in the step S1 is by propene carbonate, cyclohexanone, acetone, butanone, N-methyl pyrrolidone, N, dinethylformamide, N, one or more compositions in N-dimethylacetylamide and the dibutyl phthalate.
9, the preparation method of colloidal state polymer battery is characterized in that, comprises the steps:
Step 1, prepare material: promptly prepare composite diaphragm, positive plate and negative plate, wherein, preparing the method that composite diaphragm adopts is the preparation method of any described composite diaphragm in the claim 1 to 8;
Step 2, make electric core, promptly use the ready material package of step 1 to become electric core semi-finished product, and behind perfusion electrolyte, be cured.
10, the preparation method of colloidal state polymer battery as claimed in claim 9 is characterized in that, the curing described in the step 2 is meant, with the electric core heating after having poured into electrolyte and having sealed mouth, natural cooling then; Be 150-300 second the heating time of described heating, and heating-up temperature is 80-120 ℃.
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| CNA2008102168228A CN101393975A (en) | 2008-10-10 | 2008-10-10 | Colloidal state polymer battery and composite diaphragm manufacturing method therefor |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163744A (en) * | 2011-03-07 | 2011-08-24 | 湖北能一郎新能源研究院 | Mixed polymer colloid lithium-ion battery and manufacturing method thereof |
| CN102222802A (en) * | 2010-04-15 | 2011-10-19 | 深圳市比克电池有限公司 | Method for manufacturing lithium ion battery and rolled core thereof and lithium ion battery |
| CN102509645A (en) * | 2011-09-28 | 2012-06-20 | 江苏富朗特新能源有限公司 | Super capacitor cell encapsulation method |
| CN102637902A (en) * | 2011-02-12 | 2012-08-15 | 有量科技股份有限公司 | Safe assembling method of lithium battery |
| CN102683629A (en) * | 2012-04-24 | 2012-09-19 | 奇瑞汽车股份有限公司 | Battery diaphragm, production method of diaphragm and method for producing battery using diaphragm |
| CN104617247A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Preparation method of tandem laminated lithium-sulfur battery |
| CN105406009A (en) * | 2015-12-23 | 2016-03-16 | 梁百胜 | Gel black core lithium ion battery and manufacturing method thereof |
| CN105895845A (en) * | 2014-11-21 | 2016-08-24 | 深圳市天和顺科技有限公司 | Preparation methods of gel electrolyte separator and lithium ion battery |
| CN112201851A (en) * | 2020-10-22 | 2021-01-08 | 江苏厚生新能源科技有限公司 | Solid electrolyte slurry, preparation method thereof, diaphragm and lithium battery |
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2008
- 2008-10-10 CN CNA2008102168228A patent/CN101393975A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102222802A (en) * | 2010-04-15 | 2011-10-19 | 深圳市比克电池有限公司 | Method for manufacturing lithium ion battery and rolled core thereof and lithium ion battery |
| CN102637902A (en) * | 2011-02-12 | 2012-08-15 | 有量科技股份有限公司 | Safe assembling method of lithium battery |
| CN102163744A (en) * | 2011-03-07 | 2011-08-24 | 湖北能一郎新能源研究院 | Mixed polymer colloid lithium-ion battery and manufacturing method thereof |
| CN102163744B (en) * | 2011-03-07 | 2013-11-06 | 湖北能一郎新能源研究院 | Mixed polymer colloid lithium-ion battery and manufacturing method thereof |
| CN102509645A (en) * | 2011-09-28 | 2012-06-20 | 江苏富朗特新能源有限公司 | Super capacitor cell encapsulation method |
| CN102683629A (en) * | 2012-04-24 | 2012-09-19 | 奇瑞汽车股份有限公司 | Battery diaphragm, production method of diaphragm and method for producing battery using diaphragm |
| CN102683629B (en) * | 2012-04-24 | 2015-11-18 | 奇瑞新能源汽车技术有限公司 | Battery diaphragm, this barrier film manufacture method and use this barrier film to make the method for battery |
| CN105895845A (en) * | 2014-11-21 | 2016-08-24 | 深圳市天和顺科技有限公司 | Preparation methods of gel electrolyte separator and lithium ion battery |
| CN104617247A (en) * | 2015-01-20 | 2015-05-13 | 浙江大学 | Preparation method of tandem laminated lithium-sulfur battery |
| CN105406009A (en) * | 2015-12-23 | 2016-03-16 | 梁百胜 | Gel black core lithium ion battery and manufacturing method thereof |
| CN112201851A (en) * | 2020-10-22 | 2021-01-08 | 江苏厚生新能源科技有限公司 | Solid electrolyte slurry, preparation method thereof, diaphragm and lithium battery |
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