CN102709597A - Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery - Google Patents
Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery Download PDFInfo
- Publication number
- CN102709597A CN102709597A CN2012101782670A CN201210178267A CN102709597A CN 102709597 A CN102709597 A CN 102709597A CN 2012101782670 A CN2012101782670 A CN 2012101782670A CN 201210178267 A CN201210178267 A CN 201210178267A CN 102709597 A CN102709597 A CN 102709597A
- Authority
- CN
- China
- Prior art keywords
- polymer electrolyte
- state polymer
- solid state
- full solid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 62
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title abstract description 14
- 229920001577 copolymer Polymers 0.000 claims abstract description 73
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 71
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 70
- 239000011256 inorganic filler Substances 0.000 claims abstract description 39
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 39
- 239000007787 solid Substances 0.000 claims description 127
- 150000001875 compounds Chemical class 0.000 claims description 72
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 42
- -1 dimethyl siloxane Chemical class 0.000 claims description 37
- 239000000725 suspension Substances 0.000 claims description 31
- 238000007789 sealing Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 18
- 229910052744 lithium Chemical group 0.000 claims description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 17
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 17
- 239000002245 particle Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 16
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 15
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000004513 sizing Methods 0.000 claims description 14
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 11
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 9
- ORJLWVJIEZZMSJ-UHFFFAOYSA-N N=[S+]F.[Li] Chemical compound N=[S+]F.[Li] ORJLWVJIEZZMSJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 125000004429 atom Chemical group 0.000 claims description 6
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 abstract description 25
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract 1
- 230000008025 crystallization Effects 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 40
- 238000000034 method Methods 0.000 description 34
- 239000003792 electrolyte Substances 0.000 description 18
- 238000007731 hot pressing Methods 0.000 description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 239000011244 liquid electrolyte Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001035 drying Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000010439 graphite Substances 0.000 description 6
- 229910002804 graphite Inorganic materials 0.000 description 6
- WDGKXRCNMKPDSD-UHFFFAOYSA-N lithium;trifluoromethanesulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)F WDGKXRCNMKPDSD-UHFFFAOYSA-N 0.000 description 6
- 239000007784 solid electrolyte Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- 239000006230 acetylene black Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000006258 conductive agent Substances 0.000 description 4
- 230000002950 deficient Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 229920002239 polyacrylonitrile Polymers 0.000 description 4
- 239000004926 polymethyl methacrylate Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007773 negative electrode material Substances 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- ZPOLNCDBPYJDSE-UHFFFAOYSA-N 3-[4-[bis(2-chloroethyl)amino]phenyl]-2-formamidopropanoic acid Chemical compound O=CNC(C(=O)O)CC1=CC=C(N(CCCl)CCCl)C=C1 ZPOLNCDBPYJDSE-UHFFFAOYSA-N 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000010954 inorganic particle Substances 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 150000004040 pyrrolidinones Chemical class 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 1
- 239000002227 LISICON Substances 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910015020 LiNiCoAlO2 Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 239000002228 NASICON Substances 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NOJZFGZMTUAHLD-UHFFFAOYSA-N [Li].[Cl] Chemical compound [Li].[Cl] NOJZFGZMTUAHLD-UHFFFAOYSA-N 0.000 description 1
- 238000001467 acupuncture Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000009863 impact test Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- BMANCNNUKXPJTN-UHFFFAOYSA-N lithium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonic acid Chemical compound [Li].OS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F BMANCNNUKXPJTN-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 229910001317 nickel manganese cobalt oxide (NMC) Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
Landscapes
- Secondary Cells (AREA)
Abstract
The invention discloses a composite all solid-state polymer electrolyte lithium ion battery and a preparation method of the composite all solid-state polymer electrolyte lithium ion battery, and belongs to the all solid-state polymer electrolyte preparation technology and the lithium ion battery field. The composite all solid-state polymer electrolyte lithium ion battery disclosed by the invention comprises a battery case and an electrode core, wherein the electrode core is accommodated in the battery case in a sealed way and comprises a positive electrode, a negative electrode and composite all solid-state polymer electrolytes positioned between the positive electrode and the negative electrode, and the composite all solid-state polymer electrolytes comprise dimethyl siloxane-ethylene oxide copolymers, lithium salts and nanometer inorganic fillers. Compared with the existing composite all solid-state polymer electrolytes, the composite all solid-state polymer electrolytes adopted by the invention have the advantages that base materials are the dimethyl siloxane-ethylene oxide copolymers, the regularity of the polymer chain segment is reduced, and the crystallization degree of the polymers at the surface is reduced, so higher ionic conductivity is realized at normal temperature.
Description
Technical field
The present invention relates to a kind of lithium ion battery and preparation method thereof, relate in particular to a kind of compound full solid state polymer electrolyte lithium ion battery and preparation method thereof, belong to full solid state polymer electrolyte technology of preparing and lithium ion battery field.
Background technology
Compare with other chemical power source; Lithium rechargeable battery has the performance of many excellences; High like energy density, have extended cycle life, open circuit voltage height, memory-less effect, safety non-pollution etc.; Develop rapidly through recent two decades is applied in field of portable devices such as mobile phone, notebook computer, digital camera widely.In recent years, along with the further raising of lithium ion battery energy density, its application just progressively is extended to high-tech sectors such as Aero-Space, satellite, guided missile electric automobile, and therefore, the fail safe of battery is most important.
The internal structure of commercial lithium ion battery generally includes at present: positive pole and negative pole and the liquid electrolyte and the amberplex composition of isolating both positive and negative polarity that contain lithium salts.As everyone knows, the existence of a large amount of organic liquid electrolyte has not only increased the risk of battery leakage, and will speed up the speed of battery thermal runaway under abuse conditions, and then causes the on fire or blast of battery, has serious potential safety hazard.
Adopting all solid state electrolyte is the important method that improves battery security as the electrolyte of lithium ion battery; At present; All solid state electrolyte mainly comprises two big types: the one, and inorganic solid electrolyte is like LISICON, the inorganic solid electrolyte of NASICON structure, LiX, Li
3N and derivative etc. thereof, but this electrolytelike ionic conductivity is generally than low 3～5 one magnitude of organic liquid electrolytes ionic conductivity at normal temperatures mean that battery can not high rate charge-discharge, so limit its application in lithium battery greatly; The 2nd, organic solid electrolyte based; Like polyethers system (PEO); Such electrolyte can form stable complex compound with lithium salts, is easy to realize the conduction of ion, in addition since polymeric material itself have higher plasticity and be easy to advantage such as film forming; Can be applied to the lithium ion battery of different shape; Yet because the full solid state polymer electrolyte that PEO and lithium salts form has higher crystalline phase when room temperature, formed electrolyte also can only at high temperature could use, so its practical application is restricted.The method that is commonly used to reduce PEO degree of crystallinity is to add the organic liquid plasticizer, though the adding of liquid plasticizer has improved the ionic conductivity of full solid state polymer electrolyte, has also destroyed electrolytical mechanical performance and has increased it and the activity of cathode of lithium material simultaneously; Life-span (H.J.Walls, J.Zhou, the J.A.Yerian of battery have been reduced; Et al.J.Power Sources; 2000,89, (2): 156-162).
In recent years, mechanical property and ionic conductivity in order to improve full solid state polymer electrolyte add inorganic material particle in full solid state polymer electrolyte, like Chinese patent CN03136183.8 with inorganic oxide (montmorillonite, SiO
2Or ZnO) joins (PEO) in the polyethylene glycol oxide solid electrolyte, prepared conductivity and be about 3 * 10
-4The full solid state polymer electrolyte of S/cm (60 ℃ condition under); Chinese patent CN200610036632.9 joins (PEO) in the polyethylene glycol oxide solid electrolyte with the mesopore molecular sieve of modification, has prepared conductivity and has been about 1 * 10
-4The full solid state polymer electrolyte of S/cm (60 ℃ condition under).
But there is following defective in all solid state electrolyte of above-mentioned prior art and preparation method thereof: at first, the polyethylene glycol oxide solid electrolyte at room temperature has higher degree of crystallinity, so ionic conductivity is lower under the electrolyte room temperature; Secondly, in order to improve the low and bad problem of mechanical property of ionic conductivity, need to add a large amount of inorganic nano-fillers, well-known, the difficult dispersion of nano particle is prone to reunite, and not only influences electrolytical consistency but also is unfavorable for large-scale production; At last, also there is the bad and low defective of electrochemical stability of thermal stability in all solid state electrolyte of this system.
Summary of the invention
The objective of the invention is to solve defectives such as all solid state electrolyte ionic conductivity is low in the prior art, mechanical property is bad; A kind of compound full solid state polymer electrolyte lithium ion battery is provided, makes compound all solid state polyeletrolyte lithium ion battery ionic conductivity height, good mechanical property, Heat stability is good and electrochemical stability at normal temperatures.
Another one purpose of the present invention provides a kind of preparation method of above-mentioned compound full solid state polymer electrolyte lithium ion battery, and it is high to make that the above-mentioned compound full solid state polymer electrolyte lithium ion battery for preparing has consistency height, good stability and production efficiency.
In order to realize the foregoing invention purpose, technical scheme of the present invention is following:
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer P (DMS-CO-EO), lithium salts and nanometer inorganic filler.
The dimethyl siloxane among dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) and the mass ratio of oxirane are 3:7～7:3.
The number-average molecular weight of dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) is 5 * 10
5～1 * 10
6
The mass ratio of O atom and Li atom is 6～25:1 in dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) and the lithium salts, and described nanometer inorganic filler accounts for 5～10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Lithium salts of the present invention is a kind of or arbitrary proportion multiple in lithium hexafluoro phosphate, LiBF4, hexafluoroarsenate lithium, lithium perchlorate, trifluoromethyl sulfonic acid lithium, perfluoro butyl sulfonic acid lithium, lithium aluminate, chlorine lithium aluminate, fluoro sulfimide lithium, lithium chloride and the lithium iodide.
Above-mentioned lithium salts is preferably two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
Nanometer inorganic filler of the present invention is: titanium oxide (TiO
2), zirconia (ZrO
2), alundum (Al (Al
2O
3) and magnesia (MgO) in a kind of or arbitrary proportion multiple.
The particle diameter of above-mentioned inorganic filler is 30～70nm.
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises conventional anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, it is characterized in that: described compound full solid state polymer electrolyte prepares and is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving; (arbitrary proportion)
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer P (DMS-CO-EO), stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Be dissolved as under the room temperature being stirred to described in the steps A and stir 10～30min.
In the ultrasonic jitter time described in the step B is 10～60min.
In the stirring described in the step C is to stir 30min～2h down at 60～90 ℃.
At the evaporative removal solvent described in the step D is at 60 ℃, and vacuum degree is-the down dry 16～24h of 85KPa.
Suspension is being placed the polytetrafluoroethylene mould described in the step D, directly be clipped between the battery plus-negative plate at 0.1～2MPa, making battery plus-negative plate bonding under 60～120 ℃ with the polytetrafluoroethylene mould that suspension is housed.
Beneficial effect of the present invention is following:
1, compares with existing composite solid polymer dielectric; The composite solid polymer dielectric basis material that the present invention adopts is that dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) is because the regularity decline of polymer segment; Its crystallinity of polymer of surface descends, so has higher ionic conductivity under the normal temperature;
2, composite solid polymer dielectric of the present invention contains the nano grade inorganic filler, owing to have higher specific surface area, can improve the mechanical property and its ionic conductivity of raising of full solid state polymer electrolyte significantly;
4, adopt the prepared lithium ion battery of the present invention to have higher fail safe.
5, the dimethyl siloxane among dimethyl siloxane of the present invention-ethylene oxide copolymer P (DMS-CO-EO) and the mass ratio of oxirane are 3:7～7:3; Adopt this proportion can increase the randomness of polymer molecular chain; Also mean and to reduce crystallinity of polymer, improve the ionic conductivity of polymer itself.
6, nanometer inorganic filler of the present invention accounts for 5～10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass; The particle diameter of inorganic filler is 30～70nm; Adopt this parameter area can take into account the raising of ionic conductivity, take into account the raising of mechanical property simultaneously.
7, lithium salts of the present invention is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium, can significantly improve conductivity.
8, nano inorganic particle and polymer stir together in the prior art, and the defective of existence is after polymer joins, and the viscosity of whole suspension can sharply increase; Nano particle is difficult in and obtains in the full-bodied environment disperseing, and among the preparation method of the present invention, the nano inorganic particle is independent dispersion; So dispersiveness is better and efficient is higher, and polymer dissolution of the present invention is at 60～90 ℃ of completion down, dissolved efficiency height like this; Practice thrift cost, improved production efficiency.
Embodiment
Embodiment 1
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
Compare with existing composite solid polymer dielectric; The composite solid polymer dielectric basis material that the present invention adopts is that dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) is because the regularity decline of polymer segment; Its crystallinity of polymer of surface descends, so has higher ionic conductivity under the normal temperature.
Embodiment 2
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
The dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 7:3.
The mass ratio of O atom and Li atom is 6:1 in described dimethyl siloxane-ethylene oxide copolymer and the lithium salts, and described nanometer inorganic filler accounts for 5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 30nm.
Embodiment 3
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
The dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:7.
The mass ratio of O atom and Li atom is 25:1 in described dimethyl siloxane-ethylene oxide copolymer and the lithium salts, and described nanometer inorganic filler accounts for 10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 70nm.
Embodiment 4
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
The dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 21:29.
The mass ratio of O atom and Li atom is 15.5:1 in described dimethyl siloxane-ethylene oxide copolymer and the lithium salts, and described nanometer inorganic filler accounts for 7.5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 50nm.
Embodiment 5
A kind of compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
The dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:4.
The mass ratio of O atom and Li atom is 20:1 in described dimethyl siloxane-ethylene oxide copolymer and the lithium salts, and described nanometer inorganic filler accounts for 8.5% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
Described lithium salts is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
The particle diameter of described inorganic filler is 42nm.
Embodiment 6
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Embodiment 7
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Be dissolved as under the room temperature being stirred to described in the steps A and stir 10min.
In the ultrasonic jitter time described in the step B is 10min.
In the stirring described in the step C is to stir 30min down at 60 ℃.
At the evaporative removal solvent described in the step D is at 60 ℃, vacuum degree is-85KPa under dry 16h.
Embodiment 8
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Be dissolved as under the room temperature being stirred to described in the steps A and stir 30min.
In the ultrasonic jitter time described in the step B is 60min.
In the stirring described in the step C is to stir 2h down at 90 ℃.
At the evaporative removal solvent described in the step D is at 60 ℃, vacuum degree is-85KPa under dry 24h.
Embodiment 9
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Be dissolved as under the room temperature being stirred to described in the steps A and stir 20min.
In the ultrasonic jitter time described in the step B is 35min.
In the stirring described in the step C is to stir 1.25h down at 75 ℃.
At the evaporative removal solvent described in the step D is at 60 ℃, vacuum degree is-85KPa under dry 20h.
Embodiment 10
A kind of preparation method of compound full solid state polymer electrolyte battery; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
Be dissolved as under the room temperature being stirred to described in the steps A and stir 26min.
In the ultrasonic jitter time described in the step B is 18min.
In the stirring described in the step C is to stir 1.6h down at 81 ℃.
At the evaporative removal solvent described in the step D is at 60 ℃, vacuum degree is-85KPa under dry 21h.
Embodiment 11
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate according to (O/Li)=6, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 * 10
5, the mass ratio of dimethyl siloxane and oxirane is 1: 9; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 0.5% nano titanium oxide (TiO
2), wherein the particle diameter of titanium dioxide is 10nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano titanium oxide (TiO after the weighing
2) add ultrasonic dispersing 10min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 30min;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 16h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 5.3 * 10 then
-4S/cm.
Embodiment 12
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate according to (O/Li)=25, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 2 * 10
6, the mass ratio of dimethyl siloxane and oxirane is 9: 1; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 20% nano titanium oxide (TiO
2), wherein the particle diameter of titanium dioxide is 100nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano titanium oxide (TiO after the weighing
2) add ultrasonic dispersing 60min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 2h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 24h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 6.7 * 10 then
-4S/cm.
Embodiment 13
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and lithium perchlorate according to (O/Li)=16, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 2 * 10
6, the mass ratio of dimethyl siloxane and oxirane is 3: 7; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 10% nano titanium oxide (TiO
2), wherein the particle diameter of titanium dioxide is 50nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano titanium oxide (TiO after the weighing
2) add ultrasonic dispersing 30min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 9.1 * 10 then
-4S/cm.
Embodiment 14
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium according to (O/Li)=16, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 5 * 10
5, the mass ratio of dimethyl siloxane and oxirane is 7: 3; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 8% nano-aluminium oxide (Al
2O
3), wherein the particle diameter of alundum (Al is 30nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano-aluminium oxide (Al after the weighing
2O
3) add ultrasonic dispersing 30min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 1.2 * 10 then
-3S/cm.
Embodiment 15
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium according to (O/Li)=12, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 5 * 10
5, the mass ratio of dimethyl siloxane and oxirane is 5: 5; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 8% nano magnesia (MgO), and wherein magnesian particle diameter is 40nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: the lithium salts nano magnesia (MgO) after the weighing is added ultrasonic dispersing 10min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1.5h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 9.9 * 10 then
-4S/cm.
Embodiment 16
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium according to (O/Li)=12, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 * 10
6, the mass ratio of dimethyl siloxane and oxirane is 5: 5; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 5% nano zircite (ZrO
2), wherein zirconic particle diameter is 20nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano zircite (ZrO after the weighing
2) add ultrasonic dispersing 30min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 2.1 * 10 then
-3S/cm.
Embodiment 17
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium according to (O/Li)=16, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 * 10
6, the mass ratio of dimethyl siloxane and oxirane is 4: 6; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 5% nano zircite (ZrO
2), wherein zirconic particle diameter is 20nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano zircite (ZrO after the weighing
2) add ultrasonic dispersing 30min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 2.7 * 10 then
-3S/cm.
Embodiment 18
At first, take by weighing a certain amount of dimethyl siloxane-ethylene oxide copolymer (P (DMS-CO-EO)) and trifluoromethyl sulfonic acid lithium according to (O/Li)=16, wherein the number-average molecular weight of dimethyl siloxane-ethylene oxide copolymer is 1 * 10
6, the mass ratio of dimethyl siloxane and oxirane is 6: 4; Next mass percent that takes by weighing lithium salts and dimethyl siloxane-ethylene oxide copolymer summation is 5% nano zircite (ZrO
2), wherein zirconic particle diameter is 20nm;
Dissolving lithium salts: the lithium salts after the weighing is joined in the acetonitrile solution, at room temperature stir 30min;
Disperse inorganic filler: with the lithium salts nano zircite (ZrO after the weighing
2) add ultrasonic dispersing 30min in the above-mentioned solution;
Dissolve polymer: the dimethyl siloxane-ethylene oxide copolymer after the weighing is joined in the above-mentioned suspension stirring at room 1h;
Dry: above-mentioned solution is watered in the polytetrafluoroethylene mould, and dry 18h in 60 ℃ of vacuum environments with-85kpa obtains compound full solid state polymer electrolyte, and prepared dielectric film thickness is 120 microns.The ionic conductivity under 60 ℃ of specimen is 3.1 * 10 then
-3S/cm.
Embodiment 19
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The preparation method of lithium rechargeable battery is following processing step:
The preparation of A, anode sizing agent: be total to the technology known with LiCoO according to those skilled in the art
2,Acetylene black PVDF and NMP mix;
The preparation of B, cathode size: be total to the technology of knowing according to those skilled in the art graphite, acetylene black, PVDF and NMP are mixed;
The preparation of C, positive pole: be total to the technology anode sizing agent of knowing that steps A is prepared according to those skilled in the art and evenly be coated in collection liquid surface, 50 microns of coating thicknesss;
The preparation of D, negative pole: be total to the technology anode sizing agent of knowing that step B is prepared according to those skilled in the art and evenly be coated in collection liquid surface, 50 microns of coating thicknesss;
The preparation of E, full solid state polymer electrolyte suspension: the method according to embodiment 1～18 prepares all solid state polyeletrolyte suspension;
F, full solid state polymer electrolyte: the full solid state polymer electrolyte suspension that step e is prepared evenly is coated in anodal surface or negative terminal surface;
H, drying: with dry 16h under 60 ℃ of following vacuum conditions of step F full solid state polymer electrolyte, described vacuum degree is-85kpa;
I, heat treatment: after positive pole and the negative pole that will contain full solid state polymer electrolyte replaced lamination, at pressure 0.2MPa, 60 ℃ of following hot pressing 1min of temperature processed pole piece;
J, heat-sealing: adopt method known in those skilled in the art, the pole piece among the step C is put into aluminum plastic film bag and heat-sealing, be prepared into electric core;
K, once change into: adopt method known in those skilled in the art, adopt the 0.05C electric current that above-mentioned electric core is charged to the 70%SOC attitude;
L, secondary heat treatment: the electric core after will once changing into is 0.2MPa at pressure, and temperature is 60 ℃ of pressurization baking 3h down, obtains lithium rechargeable battery.
M, partial volume: the method that adopts those skilled in the art to know altogether tests out the capacity (rated capacity is 50mAh) of battery.
Comparative Examples 1
Employing prepares lithium ion battery with embodiment 19 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 20
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 100 ℃; Thermal pressure 1.0MPa in the step (I), hot pressing time is 10min; Thermal pressure 1.0MPa in the step (L), hot pressing time is 12h, temperature is 100 ℃.
Comparative Examples 2
Employing prepares lithium ion battery with embodiment 20 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 21
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 75 ℃; Thermal pressure 0.4MPa in the step (I), hot pressing time is 3min; Thermal pressure 0.4MPa in the step (L), hot pressing time is 4h, temperature is 75 ℃.
Comparative Examples 3
Employing prepares lithium ion battery with embodiment 21 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 22
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 85 ℃; Thermal pressure 0.6MPa in the step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in the step (L), hot pressing time is 8h, temperature is 85 ℃.
Comparative Examples 4
Employing prepares lithium ion battery with embodiment 22 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 23
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 85 ℃; Thermal pressure 0.6MPa in the step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in the step (L), hot pressing time is 8h, temperature is 85 ℃.
Comparative Examples 5
Employing prepares lithium ion battery with embodiment 23 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 24
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 85 ℃; Thermal pressure 0.6MPa in the step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in the step (L), hot pressing time is 8h, temperature is 85 ℃.
Comparative Examples 6
Employing prepares lithium ion battery with embodiment 24 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 25
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 85 ℃; Thermal pressure 0.6MPa in the step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in the step (L), hot pressing time is 8h, temperature is 85 ℃.
Comparative Examples 7
Employing prepares lithium ion battery with embodiment 25 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 26
A kind of lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Said pole piece comprises positive pole, negative pole and the full solid state polymer electrolyte between positive pole and negative pole, and said full solid state polymer electrolyte is the prepared full solid state polymer electrolyte of the method for embodiment 1～18.
The cell production process process is identical with embodiment 19, and different is: be 24h drying time in the step (H), and temperature is 85 ℃; Thermal pressure 0.6MPa in the step (I), hot pressing time is 5min; Thermal pressure 0.6MPa in the step (L), hot pressing time is 8h, temperature is 85 ℃.
Comparative Examples 8
Employing prepares lithium ion battery with embodiment 26 identical methods, and different is that electrolyte is business-like liquid electrolyte.
Embodiment 27
The security performance test
Embodiment 19～26 is 50mAh (0.1C) with Comparative Examples 1～8 prepared cell capacity.Under the room temperature, the lithium ion battery that respectively selects 6 embodiment 19～26 and Comparative Examples 1～8 to make, and battery charged with 0.1mAh/cm2, upper voltage limit 4.2V, cut-off current is 0.05C, does acupuncture, 150 ℃ of furnace temperature (1h) and impact test respectively after being full of electricity.Testing standard is with reference to U.S. UL standard, through standard for not on fire, do not explode (*: expression is not passed through; Zero: expression is passed through).As shown in table 1.
Table 1
Can find out that from embodiment 11～18 ionic conductivity of the full solid state polymer electrolyte that the present invention is prepared reaches 10
-3More than the S/cm, near the level of the ionic conductivity of liquid electrolyte; Can find out that with Comparative Examples 1～8 fail safe of adopting this full solid state polymer electrolyte is apparently higher than liquid state electrolyte battery from embodiment 19～26 in addition.
Embodiment 28
Positive pole of the present invention is meant and evenly is coated in anode sizing agent on the collector; Thickness is 10～50 microns; The preparation method of slurry is a technology known in those skilled in the art, is about to positive active material, conductive agent, binding agent and solvent and evenly gets final product.
Positive active material of the present invention is: several kinds of a kind of or arbitrary proportion among LiCoO2, LiFePO4, LiNiO2, LiNiCoAlO2, LiMn2O4 and the LiNiMnCoO2, preferred LiFePO4 or LiMn2O4.
Conductive agent of the present invention is: several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite, contain flake graphite under the preferable case.
Binding agent of the present invention is: one or more in polyvinylidene fluoride and copolymer thereof (PVDF), hexafluoropropylene-vinylidene (HFP-PVDF), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polystyrene (PS), the polymethyl methacrylate (PMMA).
Solvent of the present invention is a n-formyl sarcolysine base pyrrolidones (NMP).
Negative pole of the present invention is meant and evenly is coated in cathode size on the collector; Thickness is 10～50 microns; The preparation method of slurry is a technology known in those skilled in the art, is about to negative electrode active material, conductive agent, binding agent and solvent and evenly gets final product.
Negative electrode active material of the present invention is: several kinds of a kind of or arbitrary proportion in Delanium, native graphite, agraphitic carbon, hard carbon or the lithium titanate.
Conductive agent of the present invention is: several kinds of a kind of or arbitrary proportion in carbon black, acetylene black, carbon fiber, the flake graphite, contain flake graphite under the preferable case.
Binding agent of the present invention is: one or more in polyvinylidene fluoride and copolymer thereof (PVDF), hexafluoropropylene-vinylidene (HFP-PVDF), polyacrylonitrile (PAN), polyvinyl chloride (PVC), polystyrene (PS), the polymethyl methacrylate (PMMA);
Solvent of the present invention is a n-formyl sarcolysine base pyrrolidones (NMP).
In addition, negative pole of the present invention also can be metal lithium sheet.
The preparation method of above-mentioned a kind of lithium rechargeable battery is characterized in that: comprise following processing step:
The preparation of A, anode sizing agent: be total to the technology of knowing according to those skilled in the art positive active material and composition are mixed;
The preparation of B, cathode size: be total to the technology of knowing according to those skilled in the art negative electrode active material and composition are mixed;
The preparation of C, positive pole: be total to the technology anode sizing agent of knowing that steps A is prepared according to those skilled in the art and evenly be coated in collection liquid surface, 50～150 microns of coating thicknesss;
The preparation of D, negative pole: be total to the technology anode sizing agent of knowing that step B is prepared according to those skilled in the art and evenly be coated in collection liquid surface, 50～150 microns of coating thicknesss;
The preparation of E, full solid state polymer electrolyte suspension: the method to specifications prepares all solid state polyeletrolyte suspension;
F, full solid state polymer electrolyte: the full solid state polymer electrolyte suspension that step e is prepared evenly is coated in anodal surface or negative terminal surface;
H, drying: with the down dry 16～24h of 60 ℃ of following vacuum conditions of step F full solid state polymer electrolyte, described vacuum degree is-85kpa;
I, heat treatment: after positive pole and the negative pole that will contain full solid state polymer electrolyte replaces lamination; At pressure 0.2～1.0MPa (preferred 0.4～0.6 MPa); Temperature 60～100 ℃ (preferred 75～85 ℃) down hot pressing 1min～10min (preferred 3～5min), process pole piece;
J, heat-sealing: adopt method known in those skilled in the art, the pole piece among the step C is put into aluminum plastic film bag and heat-sealing, be prepared into electric core;
K, once change into: adopt method known in those skilled in the art, adopt the 0.05C electric current that above-mentioned electric core is charged to the 70%SOC attitude;
L, secondary heat treatment: the electric core after will once changing into is 0.2～1.0MPa (preferred 0.4～0.6 MPa) at pressure, and temperature is 60～100 ℃ (preferred 75～85 ℃) pressurization baking 3～12h (preferred 4～8 h) down, obtains lithium rechargeable battery.
M, partial volume: the method that adopts those skilled in the art to know altogether tests out the capacity of battery.
What need further specify is, if negative pole is a metal lithium sheet, the preparation method of above-mentioned a kind of lithium rechargeable battery, its characteristic do not comprise step B and step D.
Claims (10)
1. compound full solid state polymer electrolyte lithium ion battery; Comprise battery case and pole piece; Described pole piece sealing is contained in the battery case; Described pole piece comprises positive pole, negative pole and the compound full solid state polymer electrolyte between positive pole and negative pole, it is characterized in that: described compound full solid state polymer electrolyte comprises dimethyl siloxane-ethylene oxide copolymer, lithium salts and nanometer inorganic filler.
2. a kind of compound full solid state polymer electrolyte lithium ion battery according to claim 1, it is characterized in that: the dimethyl siloxane in described dimethyl siloxane-ethylene oxide copolymer and the mass ratio of oxirane are 3:7～7:3.
3. a kind of compound full solid state polymer electrolyte lithium ion battery according to claim 1 and 2; It is characterized in that: the mass ratio of O atom and Li atom is 6～25:1 in described dimethyl siloxane-ethylene oxide copolymer and the lithium salts, and described nanometer inorganic filler accounts for 5～10% of lithium salts and dimethyl siloxane-ethylene oxide copolymer gross mass.
4. a kind of compound full solid state polymer electrolyte lithium ion battery according to claim 1 and 2 is characterized in that: described lithium salts is two kinds of one or any mixed in lithium perchlorate and the fluoro sulfimide lithium.
5. a kind of compound full solid state polymer electrolyte lithium ion battery according to claim 1, it is characterized in that: the particle diameter of described inorganic filler is 30～70nm.
6. the preparation method of a kind of compound full solid state polymer electrolyte battery according to claim 1; Processing step comprises anode sizing agent and cathode size preparation, positive pole and negative pole preparation, compound full solid state polymer electrolyte preparation, heat treatment, heat-sealing, once changes into, secondary heat treatment and partial volume, and it is characterized in that: described compound full solid state polymer electrolyte preparation is specially:
A, lithium salts is joined in the acetonitrile solvent, be stirred to dissolving;
B, nanometer inorganic filler is joined in the steps A solution, ultrasonic dispersion back is stirred and is formed slurry;
C, in the prepared slurry of step B, add dimethyl siloxane-ethylene oxide copolymer, stir, form suspension;
D, the suspension among the step C is coated in anode surface, GND surface or places the polytetrafluoroethylene mould, directly be clipped between the battery plus-negative plate, the evaporative removal solvent obtains compound full solid state polymer electrolyte.
7. the preparation method of a kind of compound full solid state polymer electrolyte battery according to claim 6 is characterized in that: be dissolved as under the room temperature being stirred to described in the steps A and stir 10～30min.
8. the preparation method of a kind of compound full solid state polymer electrolyte battery according to claim 6 is characterized in that: in the ultrasonic jitter time described in the step B is 10～60min.
9. the preparation method of a kind of compound full solid state polymer electrolyte battery according to claim 6 is characterized in that: be stirring 30min～2h under 60～90 ℃ in the stirring described in the step C.
10. the preparation method of a kind of compound full solid state polymer electrolyte battery according to claim 6 is characterized in that: at the evaporative removal solvent described in the step D is at 60 ℃, and vacuum degree is-the down dry 16～24h of 85KPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178267.0A CN102709597B (en) | 2012-06-01 | 2012-06-01 | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210178267.0A CN102709597B (en) | 2012-06-01 | 2012-06-01 | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102709597A true CN102709597A (en) | 2012-10-03 |
| CN102709597B CN102709597B (en) | 2015-03-25 |
Family
ID=46902228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210178267.0A Active CN102709597B (en) | 2012-06-01 | 2012-06-01 | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102709597B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN104183865A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Lithium secondary battery |
| WO2015096619A1 (en) * | 2013-12-24 | 2015-07-02 | 江苏华东锂电技术研究院有限公司 | Preparation method for polymer lithium ion battery |
| CN104993139A (en) * | 2015-06-17 | 2015-10-21 | 北京大学深圳研究生院 | Compound silicate all-solid-state battery and preparation method thereof |
| CN105742713A (en) * | 2014-12-12 | 2016-07-06 | 东莞新能源科技有限公司 | All-solid-state polymer lithium battery |
| CN106941189A (en) * | 2017-03-15 | 2017-07-11 | 东北师范大学 | A kind of method that all solid state electrolyte is prepared based on original position |
| CN107482177A (en) * | 2017-07-03 | 2017-12-15 | 华中科技大学 | A kind of Te/C all-solid-state batteries and preparation method thereof |
| CN108155410A (en) * | 2017-12-19 | 2018-06-12 | 成都亦道科技合伙企业（有限合伙） | Solid electrolyte structure and preparation method thereof, lithium battery |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN110212241A (en) * | 2019-06-12 | 2019-09-06 | 哈尔滨工业大学 | A kind of solid electrolyte membrane and its preparation process and application |
| CN110224180A (en) * | 2019-04-30 | 2019-09-10 | 河北神州巨电新能源科技开发有限公司 | A kind of extraction process of new polymers lithium battery |
| CN110832687A (en) * | 2018-03-27 | 2020-02-21 | 株式会社Lg化学 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| CN111682258A (en) * | 2020-07-09 | 2020-09-18 | 常州赛得能源科技有限公司 | Dielectric electrolyte, lithium ion battery and preparation method thereof |
| CN113258172A (en) * | 2021-04-19 | 2021-08-13 | 中国科学院青岛生物能源与过程研究所 | Solid electrolyte suitable for room-temperature all-solid-state zinc-air battery and preparation method thereof |
| JP7450299B2 (en) | 2020-06-10 | 2024-03-15 | 華南理工大学 | Composite polymer solid electrolyte material and its preparation method and use |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454929A (en) * | 2003-05-19 | 2003-11-12 | 清华大学 | Composite solid polymer electrolyte for secondary lithium cell and preparing method thereof |
-
2012
- 2012-06-01 CN CN201210178267.0A patent/CN102709597B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1454929A (en) * | 2003-05-19 | 2003-11-12 | 清华大学 | Composite solid polymer electrolyte for secondary lithium cell and preparing method thereof |
Non-Patent Citations (2)
| Title |
|---|
| C. POLO FONSECA ET AL.: "《Characterization of polymer electrolytes based on poly(dimethyl siloxane-co-ethylene oxide)》", 《JOURNAL OF POWER SOURCES》 * |
| K. NAGAOKA ET AL.: "《High ionic conductivity in poly(dimethyl siloxane-co-ethylene oxide) dissolving lithium perchlorate》", 《J. POLYM. SCI.》 * |
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107978792A (en) * | 2013-05-24 | 2018-05-01 | 苏州宝时得电动工具有限公司 | Lithium secondary battery |
| CN104183865A (en) * | 2013-05-24 | 2014-12-03 | 苏州宝时得电动工具有限公司 | Lithium secondary battery |
| CN103647107A (en) * | 2013-11-28 | 2014-03-19 | 中国东方电气集团有限公司 | All-solid-state electrolyte membrane of lithium ion battery and preparation method thereof |
| CN103647107B (en) * | 2013-11-28 | 2016-02-03 | 中国东方电气集团有限公司 | For the dielectric film and preparation method thereof of all-solid lithium-ion battery |
| WO2015096619A1 (en) * | 2013-12-24 | 2015-07-02 | 江苏华东锂电技术研究院有限公司 | Preparation method for polymer lithium ion battery |
| CN105742713B (en) * | 2014-12-12 | 2020-08-28 | 东莞新能源科技有限公司 | All-solid-state polymer lithium battery |
| CN105742713A (en) * | 2014-12-12 | 2016-07-06 | 东莞新能源科技有限公司 | All-solid-state polymer lithium battery |
| CN104993139A (en) * | 2015-06-17 | 2015-10-21 | 北京大学深圳研究生院 | Compound silicate all-solid-state battery and preparation method thereof |
| CN106941189A (en) * | 2017-03-15 | 2017-07-11 | 东北师范大学 | A kind of method that all solid state electrolyte is prepared based on original position |
| CN107482177B (en) * | 2017-07-03 | 2019-09-13 | 华中科技大学 | A kind of Te/C all-solid-state battery and preparation method thereof |
| CN107482177A (en) * | 2017-07-03 | 2017-12-15 | 华中科技大学 | A kind of Te/C all-solid-state batteries and preparation method thereof |
| CN108155410A (en) * | 2017-12-19 | 2018-06-12 | 成都亦道科技合伙企业（有限合伙） | Solid electrolyte structure and preparation method thereof, lithium battery |
| CN108232318A (en) * | 2018-01-30 | 2018-06-29 | 陕西煤业化工技术研究院有限责任公司 | A kind of production method of all solid state power lithium-ion battery |
| CN110832687A (en) * | 2018-03-27 | 2020-02-21 | 株式会社Lg化学 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| US11476498B2 (en) | 2018-03-27 | 2022-10-18 | Lg Energy Solution, Ltd. | Complex solid electrolyte membrane for all-solid-state battery and all-solid-state battery including same |
| CN110832687B (en) * | 2018-03-27 | 2023-05-05 | 株式会社Lg新能源 | Composite solid electrolyte membrane for all-solid battery and all-solid battery comprising same |
| CN110224180A (en) * | 2019-04-30 | 2019-09-10 | 河北神州巨电新能源科技开发有限公司 | A kind of extraction process of new polymers lithium battery |
| CN110212241A (en) * | 2019-06-12 | 2019-09-06 | 哈尔滨工业大学 | A kind of solid electrolyte membrane and its preparation process and application |
| JP7450299B2 (en) | 2020-06-10 | 2024-03-15 | 華南理工大学 | Composite polymer solid electrolyte material and its preparation method and use |
| CN111682258A (en) * | 2020-07-09 | 2020-09-18 | 常州赛得能源科技有限公司 | Dielectric electrolyte, lithium ion battery and preparation method thereof |
| CN113258172A (en) * | 2021-04-19 | 2021-08-13 | 中国科学院青岛生物能源与过程研究所 | Solid electrolyte suitable for room-temperature all-solid-state zinc-air battery and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102709597B (en) | 2015-03-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102709597B (en) | Composite all solid-state polymer electrolyte lithium ion battery and preparation method of composite all solid-state polymer electrolyte lithium ion battery | |
| CN108987800B (en) | Solid electrolyte, preparation method thereof and solid battery containing solid electrolyte | |
| CN106654363B (en) | A kind of composite solid polymer electrolyte and solid lithium battery | |
| CN106328992B (en) | A kind of preparation method of lithium ion battery and the lithium ion battery | |
| CN102522560B (en) | Lithium ion secondary battery and preparation method thereof | |
| CN107591536B (en) | Gel composite positive plate, preparation method thereof and method for preparing all-solid-state lithium battery | |
| WO2020073915A1 (en) | Lithium ion battery negative electrode material and non-aqueous electrolyte battery | |
| CN103700820B (en) | A kind of lithium ion selenium battery with long service life | |
| CN109755630A (en) | A kind of Recombination gel polymer dielectric preparation method and its lithium ion battery | |
| CN102244292A (en) | Lithium ion battery ionic liquid based gel polymer electrolyte as well as preparation and applications thereof | |
| CN108963332A (en) | A kind of composite solid electrolyte material and preparation method and all-solid-state battery | |
| CN103928668B (en) | Lithium ion battery and preparation method of anode material thereof | |
| CN102643450B (en) | Preparing process of microporous composite polymer battery separator | |
| CN102082259A (en) | Lithium secondary battery electrodes and production method thereof | |
| CN103151528A (en) | Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material | |
| CN103259046A (en) | Preparation method of high-rate lithium iron phosphate lithium battery capable of being rapidly charged | |
| CN102487138B (en) | Cathode slurry and preparation method thereof, cathode of lithium ion battery and lithium ion battery | |
| CN109698384A (en) | A kind of preparation method of cylindrical mixing solid-liquid lithium ion battery | |
| CN102709598B (en) | Compound all-solid polymer electrolyte and preparation method thereof | |
| CN102881883A (en) | Ternary composite cathode material of lithium battery and preparation method of ternary composite cathode material | |
| CN110606508A (en) | Novel negative electrode material preparation method and solid-state lithium ion battery thereof | |
| CN103490071B (en) | Lithium-Polyaniline Secondary Battery and preparation method thereof | |
| CN107256963A (en) | Negative material and preparation method, negative pole and the full battery of lithium ion and preparation method | |
| CN107492660A (en) | Anode sizing agent, positive plate and lithium ion battery | |
| CN103346312B (en) | The preparation method of nest-like manganese lithium phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20180423 Address after: 610000, No. 18, West core road, hi tech West District, Sichuan, Chengdu Patentee after: Dongfang Electric Co., Ltd. Address before: Jinniu District Chengdu City, Sichuan province 610036 Shu Road No. 333 Patentee before: Dongfang Electric Corporation |