CN1601797A - Method of mfg secondary lithium cell - Google Patents
Method of mfg secondary lithium cell Download PDFInfo
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- CN1601797A CN1601797A CNA031359353A CN03135935A CN1601797A CN 1601797 A CN1601797 A CN 1601797A CN A031359353 A CNA031359353 A CN A031359353A CN 03135935 A CN03135935 A CN 03135935A CN 1601797 A CN1601797 A CN 1601797A
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- secondary battery
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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
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Abstract
Polymer composite membrane of restraining tree like crystal is composed of metal composite oxides, polymer bonding agent and polymer microporous membrane. Lithium secondary battery of using the said polymer composite membrane can restrain growth of tree-like crystal of lithium effectively, playing excellent function of depolarization so as to raise charging and discharging performance, improve cycle characteristics and safe in utilization.
Description
The present invention relates to the lithium metal is the associated materials of lithium secondary battery of negative pole and the preparation method of battery thereof, and international classification number is: H01M 10/40; H01M 2/16.
Battery is made up of positive pole, electrolyte (barrier film), negative pole, shell etc.Wherein electrode material, electrolyte are its cores.
Electrode material is divided into positive electrode active materials and negative active core-shell material.In lithium battery, positive electrode mainly contains lithium salts metal oxide, chalcogenide compound etc.Negative active core-shell material mainly contains lithium metal, lithium alloy, charcoal based material, silicon based material and tin-based material etc.In all negative materials, the lithium metal quality is the lightest, and standard electrode potential is the most negative, and (3.045V), specific capacity maximum (3860mAh/g) uses lithium metal to have high energy density and high battery operated voltage as the lithium battery of electroactive material.Lithium battery also is referred to as ultimate battery thus.
As far back as the seventies in 20th century, just the lithium metal secondary batteries is studied.And in Canada in 1988 at first with column type MoS
2/ Li storage battery drops into large-scale production.But not long when this battery applications is, cause company to regain all batteries owing in use have an accident, and stop to produce.Technical Analysis shows, the principal element that influences lithium secondary battery charge and discharge cycles stability and fail safe is that the active lithium metal of chemical property causes the electrolyte solution oxidative decomposition, product forms resistive formation on the cathode of lithium surface, simultaneously, lithium ion forms large-sized dendrite or dead lithium when the electroreduction crystallization, cause lithium secondary battery to exist the problem of hidden danger and cyclical stability.
In order to solve the fail safe that cathode of lithium causes and the problem of cyclicity difference, mainly launched research at present aspect three: 1. the negative material of seeking the alternative metals lithium; 2. adopt polymer dielectric to avoid lithium metal and organic solvent reaction; 3. improve the prescription of organic bath or add additive etc.
Have fail safe and cyclicity problem because lithium metal is the secondary cell of negative pole, the negative material of seeking the alternative metals lithium becomes the key of lithium secondary battery.Lithium secondary battery cathode material has experienced by the evolution process of lithium metal to lithium alloy, raw material of wood-charcoal material, oxide, Nanoalloy, alloy material and oxide cathode material influence cycle performance owing to change in volume is excessive and also are in conceptual phase in the charge and discharge cycles process, also fail to reach the requirement of industrialization so far.Nineteen ninety Sony company is at first with the substitution material of raw material of wood-charcoal material as lithium metal, and with its industrialization.Cyclicity problem when this kind material has improved lithium metal as negative pole, but its capacity is on the low side, along with electronics miniaturization, microminiaturized development trend, that the research and development of the negative material of high-energy-density remains is very necessary.
A large amount of experiments show, cause lithium metal secondary battery fail safe and circulative key issue to be because the lack of homogeneity of chemically active lithium metal and the formed passivation layer of electrolyte solution, cause electrode interface polarizing voltage skewness, in the deposition/course of dissolution of lithium, form Li dendrite and dead lithium, and then cause problem such as short circuit.Be directed to this, the worker has carried out number of research projects both at home and abroad, the major measure of wherein taking is attributable to two aspects: the one, and adopt polymer dielectric to improve the compatibility of lithium metal and electrolyte interface, avoid or the reaction of minimizing and organic solvent, thereby improve the electrical property of battery; (CN:1322019) adopts pure solid polymer electrolyte as Chinese patent, this electrolyte and lithium metal have interface compatibility preferably, and in battery, do not have liquid organic solvent, thereby reduced the cyclical stability that improves lithium battery with the side reaction of active lithium.Though this method has some improvement to the cycle performance of lithium battery, because conductivity is low excessively under the present copolymer solid electrolyte room temperature, make the transmission of lithium ion be restricted, also can't reach the needs of practical application.Another kind is exactly to change the electrolyte solution prescription or inwardly add additive, and this method is to utilize additive to participate in the formation of passivating film, it can be formed the more stable passivating film of lithium metal, and then improve the lithium metal secondary battery cycle performance.According to the difference of additive, form the mechanism difference of passivating film, contain villiaumite (LiPF as using in the electrolyte solution
6LiBF
4LiAsF
6Deng) or add and to contain F
-The additive of ion can improve the cycle performance of lithium secondary battery, and this mainly is that the LiF that forms makes passivation layer surface smooth, thereby makes its surface voltage distribution homogenizing, improves battery performance.And organic class additive generally is adsorbed on the lithium metal surface, improves the passivating film charge transport properties.This method is according to the difference that adds additive, improvement degree difference.But the improvement effect for this kind method is very limited, also can't reach requirement of actual application at present.
Therefore improve the cyclicity of lithium (metal) secondary cell and the difficult problem that fail safe becomes domestic and international battery operated person.The technological core that solves lithium metal secondary batteries cyclicity and safety issue is exactly formation and the growth question that solves lithium secondary battery dendrite in charge and discharge process.Prepare according to crystallography and electrochemical deposition/solution principle and a kind ofly can suppress that dendrite forms and the composite membrane of growth, and solve cyclicity that dendrite produced and the performance of safety issue and raising lithium secondary battery is a purpose of the present invention.
Another object of the present invention provides a kind of lithium secondary battery manufacturing technology that suppresses the dendrite composite membrane of using.
Inhibition dendrite composite membrane in the present invention comprises following component:
White carbon, it promptly can be that the white carbon of vapor phase method production also can be the white carbon that the precipitation method are produced.
Lithium ion can embed and take off the various oxides and the composite oxide of metal of embedding.
The polymer microporous film of ion-permeable and polymer dielectric film.
The preparation method who suppresses the dendrite composite membrane is as follows:
1. the mixed that white carbon and oxide or composite oxide of metal are pressed mass ratio 1/10～10/1, ball milling is 8～48 hours in high energy ball mill; Perhaps oxide, composite oxide of metal pre-grinding added white carbon gradually and are total to ball milling with it to the required time after 4 hour.Mixture behind the ball milling adds polymer film forming adhesive and solvent furnishing slurry, and mix with homogenizer, be coated on slurry on the polymer microporous film then or on the polymer dielectric film, coating layer thickness is 10～30 μ m, promptly get and have the composite membrane that suppresses the dendrite effect.
2. precipitated silica and a certain amount of deionized water are added in the reaction bulb that has blender, add metal chloride (as: TiCl after stirring again
4ZnCl
2SnCl
2Deng), 50～80 ℃ of reactions 8～12 hours.Reaction finishes the back and filters also oven dry filtrate, 400～600 ℃ of following roastings 12 hours in Muffle furnace then.Brilliant ball mill ball milling 24 hours of using of sample after the roasting.Powder behind the ball milling adds polymer adhesive and solvent furnishing slurry and mixes with homogenizer, is coated on slurry on the polymer microporous film or on the polymer dielectric film, and coating layer thickness 10～30 μ m promptly get and have the composite membrane that suppresses the dendrite effect.
Lithium secondary battery of the present invention is made of anode pole piece, cathode pole piece, inhibition dendrite composite membrane and electrolyte solution.Except that aforesaid inhibition dendrite composite membrane preparation method, cathode pole piece adopts metal lithium bands or is the lithium deposition and the lithium alloy (lithium-aluminium alloy, lithium silicon alloy etc.) of matrix with nickel, copper, iron foil band.The preparation method of anode pole piece will can be used as the cathode material (as: LiCoO of lithium secondary battery
2, LiNiO
2, LiMn
2O
4, TiS
2, MoS
2Deng) be configured to slurry with polymer adhesive, conductive additive, be coated on then on the aluminium foil as collector.Electrolyte solution is a nonaqueous electrolyte, and its composition comprises that alkali metal salt has lithium perchlorate (LiClO
4), LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6), hexafluoroarsenate lithium (LiAsF
6) and trifluoromethayl sulfonic acid lithium (LiSO
3CF
3) etc.; Organic solvent has propene carbonate, ethylene carbonate, gamma-butyrolacton, oxolane, 1,3-dioxolanes, sulfolane, 1,2-dimethoxy-ethane, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonic ester etc. and derivative or mixture.
The manufacture method of lithium secondary battery of the present invention is anode pole piece, cathode pole piece and inhibition dendrite composite membrane three to be reeled form its structure as Fig. 1. shown in.Suppressing surface that the dendrite composite membrane contains composite oxides when reeling should be corresponding with negative terminal surface.The outer cover packaging material of this battery both can be that the steel body case also can be the aluminum plastic film flexible package.Coiling in pack into steel body case or flexible package electricity core is injected electrolyte solution and seals.
Contain the lithium secondary battery that suppresses the dendrite composite membrane and have good charge.As Fig. 2. shown in characteristics such as discharge voltage plateau height, battery capacity are big owing to suppress the dendrite composite membrane lithium secondary battery is had the effect of significant inhibition dendritic growth, therefore, improved the fail safe that discharges and recharges of lithium secondary battery.
Fig. 1 is the profile of the lithium secondary battery of composite membrane of polymer assembling of the present invention.Among Fig. 1,1 is the anode pole piece collector body, 2 is the mixture coating (1,2 common formation anode) of positive active material, conductive additive and adhesive, 3 is polymer dielectric film or polymer microporous film, 4 is the mixture coating of composite oxide of metal and polymer adhesive, and 5 are negative pole (is alloy etc. as lithium paper tinsel band, lithium).
Fig. 2 is the charge curve of composite membrane of polymer lithium second trial battery of the present invention.Wherein ordinate is LiMn in the battery
2O
4Positive electrode material specific discharge capacity (mAh/g), abscissa are the number of times (inferior) of charge and discharge cycles.
The 1.Sn that Fig. 3 makes for embodiments of the invention 2
xSi
1-xO
2Compound, 2.SnO
2/ SiO
2Mixture and 3.SiO
2The comparison of X-diffraction pattern (XRD), wherein ordinate is a diffraction peak intensity, abscissa is the angle of diffraction (2 θ).
Lithium titanate (Li
2TiO
3) first ball mill pre-grinding 12 hours of using of 100 grams, add fume colloidal silica (SiO
2) 10 the gram carried out mixing and ball milling 12 hours, add again 10 the gram SiO
2Continued ball milling 12 hours.At the polyethylene vinyl acetate with acrylonitrile graft modification is that film forming agent, toluene are to add Li in the solution of solvent
2TiO
3-SiO
2Mass ratio is 2: 1.Slurry is coated on to be used on the lithium secondary battery electrode barrier film making as microporous polypropylene membrane, polypropylene fibre felt and various polymer dielectric film has the composite membrane of polymer that suppresses the dendrite effect.
In this embodiment, can use lithium ion to embed current potential is 0～2.0 volt of (VsLi
+/ Li) various oxides and composite oxide of metal, as: Li
4Ti
5O
12, SnO
2, SnO, TiO
2, MoO
2, WO
2, Nb
2O
5, Mo
6Se
6Deng, make this composite membrane of polymer by identical method.
Under agitation join precipitated silica 100 gram in the 500 gram deionized waters and be warming up to 60～80 ℃, dropwise splash into concentration again and be 20% SnCl
2The aqueous solution 100 gram stirred under this temperature 2～4 hours, evaporated the solid carbon dioxide branch then, placed Muffle furnace 500 ℃ of roasting temperatures 12 hours.Product after roasting obtained to contain Sn in 24 hours with the ball mill ball milling
xSi
1-xO
2The SiO of component
2Mixture, wherein Sn
xSi
1-xO
2The ratio of the tin silicon matter amount in the compound is 1: 9.It is identical with embodiment 1 to utilize this mixture and polymer, adhesive to prepare the method for composite membrane of polymer.
Based on the synthetic SiO of embodiment 2
2With the oxide mixture method, substitute in the present embodiment-SnCl with other the chloride of transition metal and hydroxide
2Make and contain M
xSi
1-xO
2Component S iO
2Mixture, 0.1≤x≤0.5 and make composite membrane of polymer wherein by embodiment 1 identical method.
Fig. 3 is Sn
xSi
1-xO
2Compound, SnO
2/ SiO
2Mixture and SiO
2The comparison of X-diffraction pattern (XRD), Sn
xSi
1-xO
2The X-diffraction pattern of compound obviously is different from the SnO of same composition
2/ SiO
2The diffraction pattern of mixture.
Li
xMn
2O
4(1≤x≤2) 100 gram, conductive black 7 grams, concentration are after LA132 aqueous binder (manufacture method is seen a Chinese patent CN:1428363A) 20 grams, deionized water or 40 milliliters of mixing of distilled water of 15%, to be stirred well to all with homogenizer again.Resulting anode sizing agent is coated in aluminium foil two-sided that thickness is 20 μ m with coating machine, uses the roller grinding compacting behind the oven dry moisture.The gross thickness of positive plate is controlled at 200～300 μ m.
The active material of cathode of battery is not limited in Li in the present invention
xMn
2O
4, every active material of cathode of lithium secondary battery that is applicable to all can use, as: LiCoO
2, LiNiO
2, LiNi
xCo
1-xO
2(0≤x≤1), TiS
2, V
6O
13, MnO
2, WO
3Deng.The operating voltage of battery is at 2.0～4.0 volts.
Anodal adhesive also can use Kynoar, polytetrafluoroethylene, Kynoar-hexafluoropropylene as adhesive except present embodiment is used.
Embodiment 4
The composite membrane of polymer that embodiment 2 is made, anode pole piece and the thickness that embodiment 3 makes are that the thick lithium band of 100～150 μ m overlaps, and wherein composite membrane of polymer contains Sn
xSi
1-xO
2The surface of material contacts with the lithium surface, is rolled into required cylindrical or square with battery winder.The outer steel shell of packing into then, soldering polar ear, inject 1 mole lithium hexafluoro phosphate, vinyl carbonate, diethyl carbonate, the electrolyte solution of dimethyl carbonate ternary solvent changes into and seals sealing to battery.
Lithium secondary battery of the present invention also can use the aluminum plastic film flexible package except using the outer steel shell encapsulation.The technology of outer steel shell encapsulation and aluminum plastic film flexible package is identical with the lithium ion battery packaging technology that industry professional all is familiar with, no specific (special) requirements.
Claims (10)
1. a lithium secondary battery manufacturing technology is characterized by, and lithium secondary battery is made of with winding method the composite membrane of polymer, positive electrode, the negative material that suppress the dendrite effect, and used electrolyte is a non-aqueous electrolytic solution.
2. the preparation method with the composite membrane of polymer that suppresses the dendrite effect is characterized in that,
(1) white carbon and oxide and composite oxide of metal use polymer adhesive that mixture is sticked and coated on polymer microporous film or the polymer dielectric film in 1: 10～10: 1 ratio mix grinding then.
(2) in the aqueous dispersion suspended substance of white carbon, be added dropwise to the metal chloride that hydrolyzable reacts, its white carbon and muriatic ratio are 10: 1～1: 10,50～80 ℃ of reactions 8～12 hours, filter then and dry, filtrate is put in the Muffle furnace in 400～600 ℃ of roastings 12～24 hours, sample ball milling after the roasting 24 hours is sticked and coated on polymer microporous film or the polymer dielectric film with the powder of polymer adhesive with product again.
3. according to the preparation method of the composite membrane of polymer of claim 2, it is characterized in that said white carbon is wherein a kind of of fume colloidal silica or precipitated silica.
4. the preparation method according to the composite membrane of polymer of claim 2 is characterized in that said oxide and composite oxide of metal are SnO
2, SnO, TiO
2, MoO
2, WO
2, Nb
2O
5, Mo
6Se
6With Li
4Ti
5O
12, Li
2TiO
3The chloride that Deng, said metal chloride is transition elements is as TiCl
4, FeCl
3, ZnCl
2And SnCl
2Deng.
5. according to the preparation method of the composite membrane of polymer of claim 2, it is characterized in that, said polymer microporous film be the polymeric barrier films that is applicable to lithium secondary battery as: microporous polypropylene membrane, the double-deck microporous barrier of polypropylene, polyethylene, polypropylene mat, polyethylene felt, said polymer dielectric film are dielectric films such as the polyoxyethylene that contains metal lithium salts or non-aqueous electrolytic solution, Kynoar, vinylidene fluoride-hexafluoropropylene copolymer, polyacrylonitrile.
6. according to the lithium secondary battery manufacturing technology of claim 1, it is characterized in that said positive electrode is that the active material of cathode that is applicable to lithium secondary battery all can use, as: LiCoO
2, LiNiO
2, LiNi
xCo
1-xO
2(0≤x≤1), TiS
2, V
6O
13, MnO
2, WO
3And derivative etc.
7. according to the lithium secondary battery manufacturing technology of claim 1, it is characterized in that said negative material is the lithium band, its thickness range is 0.05～0.2mm.Or be the lithium deposition of matrix and lithium-aluminium alloy, lithium silicon alloy etc. with nickel, copper, iron foil.
8. according to the lithium secondary battery manufacturing technology of claim 1, it is characterized in that, the used electrolyte of lithium secondary battery is a non-aqueous electrolytic solution, it is a kind of by lithium perchlorate, LiBF4, lithium hexafluoro phosphate, hexafluoroarsenate lithium, trifluoromethayl sulfonic acid lithium, is dissolved in disposing in two kinds, three kinds, the four kinds mixtures of propene carbonate, ethylene carbonate, gamma-butyrolacton, methyl-sulfoxide, 1,3-dioxolanes, sulfolane, 1,2-dimethoxy-ethane, dimethyl carbonate, diethyl carbonate, ethyl-methyl carbonic ester etc. and derivative thereof forming.
9. according to the lithium secondary battery manufacturing technology of claim 1, it is characterized in that the lithium secondary battery encapsulating housing is square or cylindrical steel or be the soft packaging body of aluminum-plastic composite membrane.
10. according to claim 6, it is characterized in that the lithium secondary battery operating voltage range is 2.0～4.0 volts.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031359353A CN100483834C (en) | 2003-09-28 | 2003-09-28 | Method of mfg secondary lithium cell |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031359353A CN100483834C (en) | 2003-09-28 | 2003-09-28 | Method of mfg secondary lithium cell |
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| Publication Number | Publication Date |
|---|---|
| CN1601797A true CN1601797A (en) | 2005-03-30 |
| CN100483834C CN100483834C (en) | 2009-04-29 |
Family
ID=34659259
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|---|---|---|---|
| CNB031359353A Expired - Lifetime CN100483834C (en) | 2003-09-28 | 2003-09-28 | Method of mfg secondary lithium cell |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617433A (en) * | 2007-05-10 | 2009-12-30 | 日立麦克赛尔株式会社 | Electrochemical element and manufacture method thereof |
| CN103682295A (en) * | 2012-09-26 | 2014-03-26 | 华为技术有限公司 | Lithium ion battery negative electrode material and preparation method thereof as well as lithium ion battery negative electrode plate and lithium ion battery |
| CN105140449A (en) * | 2015-08-14 | 2015-12-09 | 中国人民解放军63971部队 | Method for protecting anode of lithium sulfur battery |
| CN105895956A (en) * | 2016-06-14 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | Safe lithium secondary battery with high energy density |
| CN106463711A (en) * | 2014-03-24 | 2017-02-22 | 康奈尔大学 | Dendrite inhibiting electrolytes for metal-based batteries |
| CN106558664A (en) * | 2015-09-25 | 2017-04-05 | 比亚迪股份有限公司 | A kind of diaphragm for lithium ion battery and preparation method thereof and lithium ion battery |
| CN110880575A (en) * | 2018-09-06 | 2020-03-13 | 中南大学 | Composite diaphragm, preparation and application thereof in lithium-sulfur battery |
| CN111106355A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Negative electrode multistage copper skeleton current collector for lithium metal battery, preparation method of current collector and battery containing current collector |
| CN111900314A (en) * | 2020-08-04 | 2020-11-06 | 中国科学院物理研究所 | Metal composite oxide coated battery diaphragm and preparation method and application thereof |
| CN112514127A (en) * | 2018-07-13 | 2021-03-16 | 南洋理工大学 | Electrochemically active intermediate layer for rechargeable batteries |
| CN113488607A (en) * | 2021-06-07 | 2021-10-08 | 暨南大学 | Preparation and application of metal zinc cathode with functional nano material modification layer |
| CN114207900A (en) * | 2019-07-29 | 2022-03-18 | 太瓦技术公司 | Phase change electrolyte separator for solid state batteries |
-
2003
- 2003-09-28 CN CNB031359353A patent/CN100483834C/en not_active Expired - Lifetime
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101617433A (en) * | 2007-05-10 | 2009-12-30 | 日立麦克赛尔株式会社 | Electrochemical element and manufacture method thereof |
| CN103682295A (en) * | 2012-09-26 | 2014-03-26 | 华为技术有限公司 | Lithium ion battery negative electrode material and preparation method thereof as well as lithium ion battery negative electrode plate and lithium ion battery |
| CN103682295B (en) * | 2012-09-26 | 2016-03-02 | 华为技术有限公司 | A kind of lithium ion battery cathode material and its preparation method, anode plate for lithium ionic cell and lithium ion battery |
| CN106463711B (en) * | 2014-03-24 | 2021-05-07 | 康奈尔大学 | Dendrite inhibiting electrolyte for metal-based batteries |
| CN106463711A (en) * | 2014-03-24 | 2017-02-22 | 康奈尔大学 | Dendrite inhibiting electrolytes for metal-based batteries |
| CN105140449A (en) * | 2015-08-14 | 2015-12-09 | 中国人民解放军63971部队 | Method for protecting anode of lithium sulfur battery |
| CN106558664A (en) * | 2015-09-25 | 2017-04-05 | 比亚迪股份有限公司 | A kind of diaphragm for lithium ion battery and preparation method thereof and lithium ion battery |
| CN105895956A (en) * | 2016-06-14 | 2016-08-24 | 东莞市联洲知识产权运营管理有限公司 | Safe lithium secondary battery with high energy density |
| CN112514127A (en) * | 2018-07-13 | 2021-03-16 | 南洋理工大学 | Electrochemically active intermediate layer for rechargeable batteries |
| CN110880575A (en) * | 2018-09-06 | 2020-03-13 | 中南大学 | Composite diaphragm, preparation and application thereof in lithium-sulfur battery |
| CN111106355A (en) * | 2018-10-25 | 2020-05-05 | 中国科学院宁波材料技术与工程研究所 | Negative electrode multistage copper skeleton current collector for lithium metal battery, preparation method of current collector and battery containing current collector |
| CN114207900A (en) * | 2019-07-29 | 2022-03-18 | 太瓦技术公司 | Phase change electrolyte separator for solid state batteries |
| CN111900314A (en) * | 2020-08-04 | 2020-11-06 | 中国科学院物理研究所 | Metal composite oxide coated battery diaphragm and preparation method and application thereof |
| CN111900314B (en) * | 2020-08-04 | 2022-02-22 | 中国科学院物理研究所 | Metal composite oxide coated battery diaphragm and preparation method and application thereof |
| CN113488607A (en) * | 2021-06-07 | 2021-10-08 | 暨南大学 | Preparation and application of metal zinc cathode with functional nano material modification layer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100483834C (en) | 2009-04-29 |
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Address after: Hi tech building, East Road, hi tech Zone, Chengdu, Sichuan Patentee after: CHENGDU ORGANIC CHEMICALS Co.,Ltd. CHINESE ACADEMY OF SCIENCES Address before: No. four, South Renmin Road, Sichuan, Chengdu province 9 Patentee before: CHENGDU ORGANIC CHEMICALS Co.,Ltd. CHINESE ACADEMY OF SCIENCES |
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| CX01 | Expiry of patent term |
Granted publication date: 20090429 |
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| CX01 | Expiry of patent term |