CN107681114A - A kind of positive plate and preparation technology and the lithium slurry battery containing the positive plate - Google Patents
A kind of positive plate and preparation technology and the lithium slurry battery containing the positive plate Download PDFInfo
- Publication number
- CN107681114A CN107681114A CN201610620726.4A CN201610620726A CN107681114A CN 107681114 A CN107681114 A CN 107681114A CN 201610620726 A CN201610620726 A CN 201610620726A CN 107681114 A CN107681114 A CN 107681114A
- Authority
- CN
- China
- Prior art keywords
- positive
- layer
- porous
- active layer
- lithium
- Prior art date
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- Granted
Links
- 239000002002 slurry Substances 0.000 title claims abstract description 81
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 63
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000005516 engineering process Methods 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 61
- 239000003792 electrolyte Substances 0.000 claims abstract description 22
- 239000000853 adhesive Substances 0.000 claims abstract description 13
- 230000001070 adhesive effect Effects 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 337
- 239000006258 conductive agent Substances 0.000 claims description 58
- 239000000463 material Substances 0.000 claims description 45
- -1 iron sulphur compound Chemical class 0.000 claims description 40
- 239000011230 binding agent Substances 0.000 claims description 36
- 238000001035 drying Methods 0.000 claims description 34
- 239000011248 coating agent Substances 0.000 claims description 28
- 238000000576 coating method Methods 0.000 claims description 28
- 239000007774 positive electrode material Substances 0.000 claims description 27
- 150000001875 compounds Chemical class 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000004744 fabric Substances 0.000 claims description 23
- 239000012044 organic layer Substances 0.000 claims description 21
- 230000006872 improvement Effects 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000835 fiber Substances 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 11
- 238000005507 spraying Methods 0.000 claims description 11
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 10
- 239000004743 Polypropylene Substances 0.000 claims description 10
- 239000004917 carbon fiber Substances 0.000 claims description 10
- 229920000573 polyethylene Polymers 0.000 claims description 10
- 229920001155 polypropylene Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 238000007641 inkjet printing Methods 0.000 claims description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 8
- 239000011368 organic material Substances 0.000 claims description 8
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- 229910045601 alloy Inorganic materials 0.000 claims description 7
- 239000004411 aluminium Substances 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000003365 glass fiber Substances 0.000 claims description 7
- 239000007769 metal material Substances 0.000 claims description 7
- 238000007738 vacuum evaporation Methods 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000004952 Polyamide Substances 0.000 claims description 6
- 238000009825 accumulation Methods 0.000 claims description 6
- 239000011149 active material Substances 0.000 claims description 6
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- 229920002647 polyamide Polymers 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920004933 Terylene® Polymers 0.000 claims description 5
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 5
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 238000010276 construction Methods 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000007731 hot pressing Methods 0.000 claims description 5
- 150000002825 nitriles Chemical class 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920000642 polymer Polymers 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 5
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- 239000004677 Nylon Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 4
- 229920006231 aramid fiber Polymers 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000011258 core-shell material Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920001778 nylon Polymers 0.000 claims description 4
- 229920002098 polyfluorene Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920000128 polypyrrole Polymers 0.000 claims description 4
- 229920000123 polythiophene Polymers 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000010935 stainless steel Substances 0.000 claims description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000007306 turnover Effects 0.000 claims description 4
- 238000003466 welding Methods 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910003002 lithium salt Inorganic materials 0.000 claims description 3
- 159000000002 lithium salts Chemical group 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 239000004014 plasticizer Substances 0.000 claims description 3
- 229920000767 polyaniline Polymers 0.000 claims description 3
- 229910021384 soft carbon Inorganic materials 0.000 claims description 3
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 229910008416 Li-Ti Inorganic materials 0.000 claims description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 2
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 claims description 2
- 229910006861 Li—Ti Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- STUKNTHDFYCZOR-UHFFFAOYSA-N [Ba+2].[O-2].[Li+] Chemical compound [Ba+2].[O-2].[Li+] STUKNTHDFYCZOR-UHFFFAOYSA-N 0.000 claims description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 claims description 2
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical class [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 claims description 2
- MWLDTCPVXXMIRC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[Al+3].[Ni++] Chemical compound [Li+].[O--].[O--].[O--].[Al+3].[Ni++] MWLDTCPVXXMIRC-UHFFFAOYSA-N 0.000 claims description 2
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical group 0.000 claims description 2
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000006260 foam Substances 0.000 claims description 2
- 239000011888 foil Substances 0.000 claims description 2
- 229910021385 hard carbon Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910002102 lithium manganese oxide Inorganic materials 0.000 claims description 2
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 claims description 2
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007747 plating Methods 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 239000005518 polymer electrolyte Substances 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000002203 pretreatment Methods 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 2
- 230000000694 effects Effects 0.000 claims 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims 1
- 150000001345 alkine derivatives Chemical class 0.000 claims 1
- 239000007767 bonding agent Substances 0.000 claims 1
- 239000008199 coating composition Substances 0.000 claims 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 claims 1
- 238000000643 oven drying Methods 0.000 claims 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 230000006641 stabilisation Effects 0.000 claims 1
- 238000011105 stabilization Methods 0.000 claims 1
- 229910021653 sulphate ion Inorganic materials 0.000 claims 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims 1
- 238000004073 vulcanization Methods 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- 238000002347 injection Methods 0.000 abstract description 4
- 239000007924 injection Substances 0.000 abstract description 4
- 238000011049 filling Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract description 2
- 238000009434 installation Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000003273 ketjen black Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 3
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- 238000012986 modification Methods 0.000 description 3
- 229920001197 polyacetylene Polymers 0.000 description 3
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 235000011194 food seasoning agent Nutrition 0.000 description 2
- 239000000499 gel Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 239000010985 leather Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002861 polymer material Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- ZSYNKHJUSDFTCQ-UHFFFAOYSA-N [Li].[Fe].P(O)(O)(O)=O Chemical compound [Li].[Fe].P(O)(O)(O)=O ZSYNKHJUSDFTCQ-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-N benzene-dicarboxylic acid Natural products OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N o-dicarboxybenzene Natural products OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The present invention provides a kind of lithium slurry battery anode slice, the positive plate includes porous afflux anode layer, positive-active layer and fixing seal in the insulated enclosure frame of porous afflux anode layer and positive-active layer surrounding, and wherein positive-active layer is between two layers of porous afflux anode layer；The positive plate is before being assembled into lithium slurry battery and injecting electrolyte, positive-active layer in positive plate contains the positive conductive particle that some or all of non-adhesive is fixed, just fluid injection forms slurry activated batteries simultaneously to battery when in use, avoid the filling requirement to special installation and environment of slurry, it is easy to deposit and the transport of battery modules, there is application prospect in large-scale energy-accumulating power station and military civilian redundant electrical power.Meanwhile the lithium slurry battery present invention also offers a kind of preparation technology of battery anode slice and containing above-mentioned positive plate.
Description
Technical field
The invention belongs to chemomotive force battery technology, and in particular to a kind of lithium slurry battery anode slice and its preparation technology,
And the lithium slurry battery containing the positive plate.
Background technology
Lithium ion battery is the novel high-energy battery using lithium intercalation compound as positive and negative pole material, with lead-acid battery, ni-mh
Battery, which is compared, has a series of advantages such as higher than energy, voltage is high, self discharge is small, good cycle and long lifespan, increasingly
It is concerned by people.
Lithium slurry battery bag contains electrode slice and electrolyte, injects after electrolyte inside the positive plate and/or negative plate of battery
Formed with electrocondution slurry, the electrocondution slurry contains the conductive particle that certain proportion suspends or precipitated in the electrolytic solution, works as battery
During by external impact or concussion, because this partially electronically conductive particle is not adhesively fixed, therefore it can move in the electrolytic solution, and
Form dynamic conductive network, what conductive particle therein can be only containing conductive agent or active material and conductive agent
Composite particles.Electrocondution slurry in lithium slurry battery can avoid electrode material fall off or loosen caused by under battery capacity
Drop and cycle life decay.
The content of the invention
The present invention provides a kind of lithium slurry battery anode slice and the lithium slurry battery containing the positive plate, and positive plate is in group
Put into lithium slurry battery and inject before electrolyte, the positive-active layer in positive plate, which contains some or all of non-adhesive, to be fixed
Positive conductive particle, positive-active layer is in leather hard or drying regime, after electrolyte injection, this part positive conductive particle
It can in the electrolytic solution move, and form dynamic conductive network.Present invention also offers the preparation work of the positive plate simultaneously
Skill.
It is as follows that the present invention provides technical scheme：
A kind of lithium slurry battery anode slice, it is close that the positive plate includes porous afflux anode layer, positive-active layer and fixation
The insulated enclosure frame of porous afflux anode layer and positive-active layer surrounding is encapsulated in, wherein positive-active layer is located at two layers of porous afflux
Between anode layer；Wherein, the positive-active layer contains the positive conductive particle that some or all of non-adhesive is fixed, it is described just
Pole conductive particle is conductive agent, or, the positive conductive particle is the compound of positive electrode active materials and conductive agent or mixed
Thing.
When the positive conductive particle is the compound or mixture of positive electrode active materials and conductive agent, the positive pole is lived
Property material and conductive agent it is compound or the mode of mixing includes Surface coating, bonding or mechanical mixture etc..
The positive-active layer contains the positive conductive particle that some or all of non-adhesive is fixed, and can be containing part
The leather hard of liquid, such as paste, pulp-like, colloidal state or gel；Preferably, the positive-active layer is to be completely dried shape
The dryness accumulation state of state, i.e. positive conductive particle, such as powder, wafer-like, compacting block etc., the porosity for accumulating state is more than
5% is less than 60%.Using the positive-active layer of drying regime, positive conductive is fully infiltrated by electrolyte after electrolyte is injected
Grain, is then internally formed electrocondution slurry in positive plate.This positive plate is suitable for production line balance, can be noted in existing lithium battery
Realized in liquid Equipment Foundations by partial reequipping, the pole piece uniformity prepared is high, more with commercial promise.
The positive-active layer includes positive conductive particle and/or binding agent, the thickness of positive-active layer for 0.5mm~
10mm, the positive conductive mean particle size are 0.05 μm~500 μm, and positive conductive particle is positive electrode active materials and conduction
The compound or mixture of agent, the mass ratio of wherein positive electrode active materials and conductive agent is preferably 20~98：80~2, and bond
The mass ratio of agent is no more than 10%.
Or the positive-active layer includes the first positive-active layer and the second positive-active layer, the thickness of positive-active layer
Spend and not less than 0.05mm and be not more than 10mm for 0.5mm~10mm, the thickness of the first positive-active layer；Wherein first just
Positive conductive particle in the active layer of pole is positioned partially or entirely in surface or the mesh of the porous anode current collector layer, and first just
Pole active layer includes positive electrode active materials, conductive agent and binding agent, positive electrode active materials:Conductive agent:Binding agent is according to mass ratio
For 59~98:1~40:1~10 is well mixed；Second positive-active layer and the first positive-active layer are in close contact, and described second
Positive-active layer includes the positive conductive particle that non-adhesive is fixed, and the positive conductive mean particle size is 0.05 μm~500 μ
M, in the case where positive conductive particle is the compound or mixture of positive electrode active materials and conductive agent, positive electrode active materials with
The mass ratio of conductive agent is preferably 0~98:100~2, and the mass ratio of binding agent is no more than 5%.That is, when it is described just
When pole active layer includes the first positive-active layer and the second positive-active layer, the positive conductive particle in the second positive-active layer can
Not contain positive electrode active materials, only contain conductive agent.
When positive-active layer includes the first positive-active layer and the second positive-active layer, due to the first positive-active layer with
The conductive contact of porous afflux anode layer is more preferable, therefore it can preferably provide the energy of battery under big multiplying power.
The positive electrode active materials of the positive-active layer are LiFePO4, lithium manganese phosphate, lithium metasilicate, ferric metasilicate lithium, sulfuric acid
Salt compound, sulphur carbon complex, sulphur simple substance, titanium sulphur compound, molybdenum sulfur compound, iron sulphur compound, doped lithium manganese oxide, lithium
Cobalt/cobalt oxide, Li-Ti oxide, lithium-barium oxide, Li, Ni, Mn oxide, lithium nickel cobalt oxides, lithium nickel cobalt aluminum oxide, lithium nickel
Aluminum oxide, lithium nickel cobalt manganese oxide, lithium iron Ni, Mn oxide and other one or more that can be in lithium intercalation compound.It is described
Binding agent is that potential window is wide and align the stable polymeric material of negative active core-shell material and electrolyte, and the polymeric material can
To be that polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyamides are sub-
Amine, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, change
Property polyolefin, polyacetylene, polypyrrole and its derivative, polythiophene and its derivative, Polyaniline and its derivative, polyparaphenylene's second
Alkene and its derivative, gather to the one or more in benzene and its derivative, polyfluorene and its derivative.The conductive agent be carbon black,
One or more in Ketjen black, graphene, CNT, carbon fiber, amorphous carbon or metallic conduction particle.
Positive conductive particle in the positive-active layer is positioned partially or entirely in the hole of porous afflux anode layer, institute
It is the electron conducting layer with through-hole structure that thickness is 0.01 μm~2000 μm to state porous afflux anode layer, its through hole porosity
For 10%~90%, pore diameter range 0.05mm~2mm.The porous afflux anode layer is metal conducting layer, the metal conducting layer
For wire netting or woven wire cloth, mesh is square, rhombus, rectangle or polygon etc.；Or metal conducting layer be with
The porous foam metal layer of loose structure；Or metal conducting layer is metallic plate or metal foil through mechanical stamping or chemical attack
Form, the material of metal conducting layer is aluminium, alloy aluminum, stainless steel, silver, tin or titanium etc., and preferably the material is aluminium.It is or more
The conductive fabric that hole afflux anode layer is electric conduction of carbon fiber cloth, wire mixes with organic fiber silk, the material of wire is copper, nickel
Or titanium etc..Or porous afflux anode layer is that surface coats conductive coating or is coated with the metal conducting layer of metallic film, conduction
Cloth, porous organic material or microporous inorganic nonmetallic materials, porous organic material include natural linen-cotton, terylene, aramid fiber, nylon,
Polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE) etc., microporous inorganic nonmetallic materials include glass fibre non-woven, ceramic fiber paper etc.,
The material of conductive coating or metallic film is aluminium, alloy aluminum, stainless steel or silver etc., and preferably the material is aluminium.Or porous collection
Stream anode layer is metal conducting layer, conductive fabric, porous organic material, inorganic non-metallic material, surface coating conductive coating or plating
There is the compound of the metal conducting layer of metallic film, conductive fabric, inorganic non-metallic material, porous organic material and polymer dielectric
Layer, polymer dielectric are electric for the gelatin polymer of polymeric matrix, liquid organic plasticizers and the compound composition of lithium salts three parts
Solve composite material.Or porous afflux anode layer is by above-mentioned any assembly that two or more are formed.
Preferably, interface improvement layer is contained at the grid of the porous afflux anode layer.The material of the interface improvement layer
Including conductive agent and binding agent, the mass ratio of binding agent and conductive agent is 0.5~20：99.5~80, or interface improvement
Layer only includes conductive agent；The conductive agent is carbon black, Ketjen black, graphene, CNT, carbon fiber, amorphous carbon or metal
One or more in conductive particle, the binding agent are that potential window is wide and to align negative active core-shell material and electrolyte stable
Polymeric material, the polymeric material can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), poly-
Terephthalate, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile,
Butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene, polyacetylene, polypyrrole and its derivative, polythiophene and its derivative,
Polyaniline and its derivative, poly-phenylene vinylene (ppv) and its derivative, gather to one in benzene and its derivative, polyfluorene and its derivative
Kind is several.
The interface improvement layer is closely compounded in the grid of the porous afflux anode layer, can improve porous afflux just
The interface performance of pole layer, reduce its interface resistance with positive-active interlayer.In the present invention, preferable interface improvement layer is very thin,
Exist only at the grid of the porous afflux anode layer, can not have to be distributed in the mesh of porous afflux anode layer.It is described
Interface improvement layer and the complex method of the porous afflux anode layer include but is not limited to vacuum evaporation, magnetron sputtering, plasma
One or more in deposition, spraying, bonding, machinery press-in, printing, inkjet printing.
When the hole of porous afflux anode layer is larger, the interface improvement layer is combined at the grid of porous afflux anode layer
When and middle dryness anode active material layer in positive conductive particle when falling into the hole of porous afflux anode layer, it may occur that
The phenomenon of material leakage, it is therefore preferred that the porous afflux anode layer also includes leakproof Porous-Organic layer, the leakproof Porous-Organic
Layer is compound in the one side or both sides of porous afflux anode layer, or when porous anode current collector layer has double-deck or sandwich construction when institute
Stating leakproof Porous-Organic layer can be arranged among porous afflux anode layer, and the presence of leakproof Porous-Organic layer can anti-leak-stopping
Material.The conductive fabric that the material of the leakproof Porous-Organic layer can mix for electric conduction of carbon fiber cloth, wire with organic fiber silk,
Or pore screen cloth, glass fiber non-woven for natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE)
Cloth, ceramic fiber paper etc. or conductive fabric, pore screen cloth, glass fibre non-woven, ceramic fiber paper surface coating conduction
Coating is coated with metallic film, and such leakproof Porous-Organic layer can play a part of afflux jointly with porous afflux anode layer,
Its aperture and thickness are respectively less than porous afflux anode layer, and scope is at 10 μm~800 μm, 0.01 μm~1000 μm of thickness, its through hole
Porosity is 10%~90%.
Further, the positive-active layer surface can add conductive layer by the mode such as filtering, spraying, so can be with
Make Conductive layer portions or be stuffed entirely with the hole of positive-active layer, so as to better ensure that the particle in positive-active layer begins
It is in eventually among conductive network.When positive-active layer includes the first positive-active layer and the second positive-active layer and the work of the second positive pole
When the positive conductive particle of property layer only contains conductive agent, the second positive-active layer becomes conductive layer in itself.
The conductive layer includes conductive agent and/or binding agent, and the mass ratio of binding agent and conductive agent is 0~10:100~
90, preferably without binding agent.The binding agent is that potential window is wide and align stable poly- of negative active core-shell material and electrolyte
Compound material, the polymeric material can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), poly- pair
Phthalic acid ester, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, fourth
Benzene rubber, sodium carboxymethylcellulose, improved polyalkene, polyacetylene, polypyrrole and its derivative, polythiophene and its derivative, gather
Aniline and its derivatives, poly-phenylene vinylene (ppv) and its derivative, gather to one kind in benzene and its derivative, polyfluorene and its derivative
Or it is several, the conductive agent is carbon black, Ketjen black, graphene, CNT, carbon fiber, amorphous carbon or metallic conduction particle
In one or more, preferably carbon fiber and other granular pattern compatible uses.
Insulated enclosure frame is provided with the edge of porous afflux anode layer-positive-active layer-porous afflux anode layer, should
Insulated enclosure frame is connected to the surrounding of above-mentioned sandwich composite construction by modes such as hot pressing, stickups.Insulated enclosure frame plays insulation
Act on and prevent positive conductive particle from the sealing function of edge seepage.The material of insulated enclosure frame is resistance to electrolysis of insulating
The polymeric material of liquid, for example, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), poly terephthalic acid
Ester, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, carboxylic
One or more in sodium carboxymethylcellulose pyce, improved polyalkene.
Preferably, the surface of positive plate can be provided with electronic isolation ion conducting positive pole separation layer and/or negative pole every
Absciss layer, the positive pole separation layer and/or negative pole separation layer are that polyethylene, polypropylene, Kynoar or other electronics are nonconducting
Porous polymer material；Or separation layer is glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper or other electricity
The composite porous material of the nonconducting inorganic non-metallic material of son and organic polymer；Or the material of separation layer uses electronics
The gel polymer electrolyte composite wood of nonconducting polymeric matrix, liquid organic plasticizers and the compound composition of lithium salts three parts
Material, further, the nonconducting porous polymer material of described electronics, inorganic non-metallic material and organic polymer it is compound more
The electrolyte or polymeric colloid material of ionic conduction are impregnated with the hole of Porous materials.
The present invention also provides a kind of preparation technology of the lithium slurry battery anode slice, it is characterised in that positive-active layer position
Among two layers of porous afflux anode layer, and prepare complete positive plate in positive-active layer contain it is some or all of non-stick
Fixed positive conductive particle is connect, is comprised the following steps：
(1), pre-treatment of raw material：Porous afflux anode layer is sprayed and is cleaned by ultrasonic using cleaning solvent, and is dried
It is dry standby；Required conductive agent, positive electrode active materials, binding agent are dried for standby；Wherein, binding agent drying temperature is less than bonding
20 DEG C of agent material softening point, drying time are no more than 2h, conductive agent and positive electrode active materials drying temperature can at 100~250 DEG C,
2~4h of drying time；
(2) positive-active layer slurry, is prepared：The positive-active material required for porous anode material layer is weighed according to proportioning
Material, conductive agent and binding agent, three is uniformly mixed to obtain positive-active layer slurry；
(3), it is coated with positive-active layer：The positive-active layer slurry obtained in above-mentioned steps (2) is uniform by coating machine
Interval is coated on the side of porous afflux anode layer so as to form multiple coating zones；
(4), section turnover：Cut into slices, cut into slices using two neighboring coating zone in step (3) as a section unit
Unit afterwards turns into quasi- pole piece, the porous afflux anode layer uncoated one of each quasi- pole piece faces outwardly from middle doubling；
(5), pressing and stoving：Suitably pressurizeed in quasi- pole piece upper and lower surface with clamping plate, pressure is 0.01~2MPa, is subsequently placed in
High temperature oven is dried, 100~140 DEG C, 2~24h of drying time of drying temperature, the natural cooling in baking oven of the quasi- pole piece after drying
To room temperature, the positive-active layer after drying in pole piece is in drying regime；
(6) edge seal：Four sides of quasi- pole piece are encapsulated using ultrasonic bonding machine welding, adding insulating frame by hot pressing obtains
To positive plate.
In the step (1), after the completion of porous afflux anode layer cleaning, drying, lead at the grid of porous afflux anode layer
Cross vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, machinery press-in, printing or one kind in inkjet printing or several
Kind mode compound interface improves layer.
In the step (1), after the completion of porous afflux anode layer cleaning, drying, in the one side of porous afflux anode layer or two
It is compounded among the bilayer or sandwich construction of side or porous afflux anode layer by way of mechanical press, bonding, coating anti-
Leak Porous-Organic layer.
In the step (2), the positive-active layer slurry includes the first positive-active layer slurry and the second positive-active
Layer slurry, wherein the first positive-active layer slurry passes through vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, machinery
One or more of modes in press-in, printing or inkjet printing are in close contact with the porous afflux anode layer, and the second positive pole is lived
Property layer slurry pass through vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, machinery press-in, printing or inkjet printing in
One or more of modes and the first positive-active layer slurry contact.
Between the step (3) and step (4), it can be added and led by way of spraying or filtering in positive-active layer surface
Electric layer.
The present invention also provides a kind of lithium slurry battery containing above-mentioned positive plate, including battery core, it is characterised in that the electricity
Core include several alternately place the positive plate and negative plate, between the positive plate and negative plate spacing be 0.05~
1mm, the spacing form separate cavities, are full of electrolyte in the separate cavities；
The positive plate include porous afflux anode layer, positive-active layer and fixing seal in porous afflux anode layer and
The insulated enclosure frame of positive-active layer surrounding, wherein positive-active layer are between two layers of porous afflux anode layer；The positive pole
Active layer contains the positive conductive particle that some or all of non-adhesive is fixed, and the positive conductive particle is conductive agent, or,
The positive conductive particle is the compound or mixture of positive electrode active materials and conductive agent；
The negative plate include porous afflux negative electrode layer, negative electrode active layer and fixing seal in porous afflux negative electrode layer and
The insulated enclosure frame of negative electrode active layer surrounding, wherein negative electrode active layer are between two layers of porous afflux negative electrode layer；The negative pole
Active layer is metal lithium sheet, or the negative electrode active layer contains the negative conductive particle that some or all of non-adhesive is fixed,
The negative conductive particle for can embedding cathode of lithium active material and conductive agent compound or mixture；It is described can embedding cathode of lithium live
Property material include graphite, hard carbon, soft carbon, kamash alloy, acieral, lithium titanate or silica-base material in one or more.
The battery battery core assembling, dehumidify and electrolyte is injected after vacuumizing, electrolyte enters separate cavities, then by just
The porous afflux anode layer of pole piece penetrates into positive-active layer, forms part or the entirely positive-active of slurry form
Layer.
Advantage of the invention is that：
Positive-active layer in the present invention is the accumulation state of positive conductive particle, is in slurry form after injection electrolyte.Just
The positive-active layer of the stacking states of pole conductive particle more facilitates the compatibility assembling and the control of pole piece uniformity of electrode slice,
Avoid the filling requirement to special installation and environment of slurry；After pole piece is assembled into battery modules, due to before electrolyte injects,
It is still the positive-active layer of the stacking states of positive conductive particle inside pole piece, just fluid injection formation slurry is same when in use for battery
When activated batteries, therefore deposit and the transport of battery modules are also convenient for, in large-scale energy-accumulating power station and military civilian redundant electrical power
With application prospect.
Brief description of the drawings
Fig. 1 is the structural representation of lithium slurry battery anode slice in the embodiment of the present invention one, wherein 101-insulating frame；
102-porous afflux anode layer；103-positive-active layer；
Fig. 2 is the structural representation of lithium slurry battery anode slice in the embodiment of the present invention two, wherein the 204-the second positive pole is lived
Property layer；205-leakproof Porous-Organic layer；206-the first positive-active layer；207-interface improvement layer；
Fig. 3 be lithium slurry battery anode slice of the present invention overall schematic, 301-positive pole ear；
Fig. 4 is that the section in lithium slurry battery anode slice preparation technology of the present invention turns down schematic diagram, wherein 401-turnover
Line；402-slice；403-section unit；
Fig. 5 is the structural representation of lithium slurry battery of the present invention, wherein 5-positive plate；6-separate cavities；7-negative plate.
Embodiment
Below in conjunction with the accompanying drawings, by embodiment, the present invention will be further described.
Embodiment one
The present embodiment provides a kind of lithium slurry battery anode slice, including porous afflux anode layer 102, positive-active layer 103
And the insulated enclosure frame 101 positioned at porous afflux anode layer and positive-active layer surrounding.In the present embodiment, the porous afflux
Anode layer 102 is aluminium net, and thickness is 2000 μm, and its through hole porosity is 50%, aperture 2mm.Wherein in positive-active layer 103 just
Pole active material:Conductive agent:Binding agent is 45 according to mass ratio:50:5 is well mixed, and wherein positive electrode active materials select phosphoric acid
Iron lithium, conductive agent select conductive carbon black, and binding agent selects Kynoar, and the thickness of positive-active layer is 10mm.
Embodiment two
The present embodiment provides a kind of lithium slurry battery anode slice, including porous afflux anode layer 102, the first positive-active layer
206th, the second positive-active layer 204 and the insulated enclosure frame 101 positioned at porous afflux anode layer and positive-active layer surrounding.This
In embodiment, interface improvement layer 207 is coated at the grid of the porous afflux anode layer, while for leakproof, in the present embodiment
Leakproof Porous-Organic layer 205 is provided with two layers of porous afflux anode layer.
In the present embodiment, porous afflux anode layer selects stainless (steel) wire, and thickness is 0.01 μm, and its through hole porosity is
90%, aperture 0.005mm.Interface improvement layer includes conductive agent and binding agent, and the mass ratio of binding agent and conductive agent is 20：80,
Wherein conductive agent selects carbon black, and binding agent selects Kynoar.
Interface improvement layer is coated in the thin layer at porous afflux anode layer grid, can improve porous afflux anode layer
Interface performance, reduces its interface resistance with positive-active interlayer, and interface improvement layer is answered by spraying with porous afflux anode layer
Close.
In the present embodiment, the hole of porous afflux anode layer is larger, and interface improvement layer 207 is combined to porous afflux anode layer
Grid at when and the first positive-active layer 206 when falling into the hole of porous afflux anode layer, it may occur that the phenomenon of material leakage,
Therefore in the present embodiment, one layer of leakproof Porous-Organic layer 205 is compounded with by roll-in between two layers of porous afflux anode layer, prevented
Leak Porous-Organic layer choosing terylene non-woven fabric.
In the present embodiment, in mesh of the part of the first positive-active layer 206 full of porous anode current collector layer, the first positive pole
Positive electrode active materials in active layer:Conductive agent:Binding agent is 90 according to mass ratio:5:5 is well mixed；Second positive-active layer
204 and first positive-active layer be in close contact, the positive conductive particle in the second positive-active layer only contains conductive agent.This implementation
In example, positive electrode active materials select cobalt acid lithium, and conductive agent selects graphene, and binding agent selects butadiene-styrene rubber and carboxymethyl cellulose
Mixture, the gross thickness of the first positive-active layer and the second positive-active layer is 3mm.
Embodiment three
The present embodiment provides a kind of lithium slurry battery anode slice, unlike embodiment two, in the second positive-active layer
Positive conductive particle to contain conductive agent and binding agent and mass ratio be 97:3, wherein conductive agent is Ketjen black and CNT
Mixture, binding agent are polyacrylonitrile.A thin layer conductive layer is coated on the surface of the second positive-active layer simultaneously, and passes through suction filtration
Mode cause Conductive layer portions or be stuffed entirely with the hole of the second positive-active layer, so as to better ensure that positive-active
Particle in layer is among conductive network all the time.In the present embodiment, conductive layer only contains conductive agent, and wherein conductive agent selects carbon
Fiber.
Example IV
The present invention provides a kind of preparation technology of above-mentioned lithium slurry battery anode slice, comprises the following steps：
(1) porous afflux anode layer is introduced into cleaning showers room and ultrasonic cleaning tank, sprayed using cleaning solvent
And ultrasonic cleaning, drying channel hot-air seasoning is then introduced, different according to porous afflux positive pole layer material, the cleaning solvent can
To be the one or more in deionized water, ethanol, acetone, watery hydrochloric acid, diluted sodium hydroxide solution.
(2) according to positive electrode active materials:Conductive agent:Binding agent mass ratio is 85:12:3 weigh and are well mixed, and obtain just
Pole active layer slurry；
(3) the positive-active layer slurry obtained in above-mentioned steps (2) uniformly intermittently, is coated on porous collection by coating machine
Flow the side of anode layer, coating thickness 0.05mm；
(4), section turnover：Using two neighboring coating zone in step (3) as a section unit 403 along slice
402 are cut into slices, and the unit after section turns into quasi- pole piece, the porous afflux anode layer of each quasi- pole piece along the doubling of turn-line 401
Uncoated one faces outwardly；
(5), pressing and stoving：Suitably pressurizeed in quasi- pole piece upper and lower surface with clamping plate, pressure is that 0.01MPa is subsequently placed in high temperature
Oven for drying, 100 DEG C, drying time 24h of drying temperature, the quasi- pole piece after drying naturally cools to room temperature in baking oven, drying
Positive conductive particle is accumulation state in the positive-active layer in pole piece afterwards；
(6) edge seal：Four sides of quasi- pole piece are encapsulated using ultrasonic bonding machine welding, adding insulating frame by hot pressing obtains
To positive plate.
Embodiment five
The present invention provides a kind of preparation technology of above-mentioned lithium slurry battery anode slice, comprises the following steps：
(1) porous afflux anode layer is introduced into cleaning showers room and ultrasonic cleaning tank, sprayed using cleaning solvent
And ultrasonic cleaning, drying channel hot-air seasoning is then introduced, different according to porous afflux positive pole layer material, the cleaning solvent can
To be the one or more in deionized water, ethanol, acetone, watery hydrochloric acid, diluted sodium hydroxide solution；
(2) one layer of leakproof Porous-Organic layer will be placed among two layers of porous afflux anode layer, is combined with each other by roll-in；
(3) configuration interface improves layer slurry, and the wherein mass ratio of binding agent and conductive agent is 5：95, and by interface improvement layer
Slurry is coated on the porous afflux anode layer side, and coating layer is located at the grid of porous afflux anode layer；
(4) positive-active layer slurry is configured, respectively according to positive electrode active materials:Conductive agent:Binding agent mass ratio is 59:
31:10 weigh and are well mixed, and obtain the first positive-active layer slurry；Weigh that conductive agent is well mixed to be used as the second positive-active
Layer；
(5), the first positive-active layer slurry obtained in above-mentioned steps (4) is uniformly intermittently coated on by coating machine more
The side of hole afflux anode layer is simultaneously in close contact with interface improvement layer, and coating thickness 0.5mm, the first positive-active layer segment fills
In the mesh of full porous afflux anode layer；The the second positive-active layer slurry obtained in above-mentioned steps (4) is equal by coating machine
Even interval is coated on the first positive-active layer surface；
(6), section turnover：Two neighboring coating zone in step (3) is cut into slices as a unit, after section
Unit turns into quasi- pole piece, the porous afflux anode layer uncoated one of each quasi- pole piece faces outwardly from middle doubling；
(7), pressing and stoving：Suitably pressurizeed in quasi- pole piece upper and lower surface with clamping plate, pressure is that 2MPa is subsequently placed in high temperature baking
Case is dried, and 140 DEG C, drying time 2h of drying temperature, the quasi- pole piece after drying naturally cools to room temperature, pole after drying in baking oven
Positive-active layer in piece is in drying regime；
(8), edge seal：Four sides of quasi- pole piece are encapsulated using ultrasonic bonding machine welding, insulating frame is added by hot pressing
Obtain positive plate.
Embodiment 6
The present embodiment provides a kind of lithium slurry battery, including battery core, and the battery core includes several positive poles alternately placed
Piece 5 and negative plate 7, spacing is 0.05~1mm between the positive plate 5 and negative plate 7, and the spacing forms separate cavities 6, described
Electrolyte is full of in separate cavities 6；5, the positive pole includes porous afflux anode layer, positive-active layer and fixing seal in more
The insulated enclosure frame of hole afflux anode layer and positive-active layer surrounding, wherein positive-active layer are located at two layers of porous afflux anode layer
Between；The positive-active layer contains the positive conductive particle that some or all of non-adhesive is fixed, the positive conductive particle
For conductive agent, or, the positive conductive particle is the compound or mixture of positive electrode active materials and conductive agent；The negative pole
Piece includes porous afflux negative electrode layer, negative electrode active layer and fixing seal in porous afflux negative electrode layer and negative electrode active layer surrounding
Insulated enclosure frame, wherein negative electrode active layer are between two layers of porous afflux negative electrode layer；The negative electrode active layer is metal lithium sheet,
Or the negative electrode active layer contains the negative conductive particle that some or all of non-adhesive is fixed, the negative conductive particle is
Can embedding cathode of lithium active material and conductive agent compound or mixture；It is described can embedding cathode of lithium active material include graphite, hard
One or more in carbon, soft carbon, kamash alloy, acieral, lithium titanate or silica-base material.
Battery battery core assembling, dehumidify and electrolyte is injected after vacuumizing, electrolyte enters separate cavities, then passes through positive plate
Porous afflux anode layer penetrate into positive-active layer, form part or entirely the positive-active layer of slurry form.
The specific embodiment of the invention is not limited to the present invention.Any those skilled in the art, do not departing from
Under technical solution of the present invention ambit, all technical solution of the present invention is made using the methods and technical content of the disclosure above
Many possible changes and modifications, or it is revised as the equivalent embodiment of equivalent variations.Therefore, it is every without departing from the technology of the present invention side
The content of case, the technical spirit according to the present invention is to any simple modifications, equivalents, and modifications made for any of the above embodiments,
Still fall within technical solution of the present invention protection in the range of.
Claims (15)
1. a kind of lithium slurry battery anode slice, the lithium slurry battery anode slice includes porous afflux anode layer, positive-active layer
And the insulated enclosure frame positioned at the porous afflux anode layer and the positive-active layer surrounding, wherein the positive-active layer
Between two layers of porous afflux anode layer, it is characterised in that：The positive-active layer contains some or all of non-stick
Fixed positive conductive particle is connect, the positive conductive particle is conductive agent, or the positive conductive particle is positive-active
The compound or mixture of material and conductive agent.
2. lithium slurry battery anode slice as claimed in claim 1, it is characterised in that：The positive-active layer is positive conductive
The accumulation state of grain, the accumulation state of the positive conductive particle include powder accumulation, wafer-like or compacting block, accumulate the hole of state
Rate is more than 5% and is less than 60%.
3. lithium slurry battery anode slice as claimed in claim 1, it is characterised in that：The positive-active layer includes the positive pole
Conductive particle and binding agent, or the positive-active layer only include the positive conductive particle, the thickness of the positive-active layer
It is 0.05 μm~500 μm to spend for 0.5mm~10mm, the positive conductive mean particle size, and the positive conductive particle is institute
The compound or mixture of positive electrode active materials and the conductive agent are stated, wherein the positive electrode active materials and the conductive agent
Mass ratio is 20~98：80~2, and the mass ratio of the binding agent is no more than 10%.
4. lithium slurry battery anode slice as claimed in claim 1, it is characterised in that：The positive-active layer includes the first positive pole
Active layer and the second positive-active layer, the thickness of the positive-active layer is 0.5mm~10mm, the first positive-active layer
Thickness is not less than 0.05mm and is not more than 10mm；The part or all of position of positive conductive particle in the first positive-active layer
In in the surface of the porous anode current collector layer or mesh, the positive electrode active materials in the first positive-active layer：Conductive agent：
Binding agent is 59~98 according to mass ratio：1~40：1~10 is well mixed；The second positive-active layer and first positive pole
Active layer is in close contact, and the second positive-active layer includes the positive conductive particle that non-adhesive is fixed, the positive conductive
Grain average grain diameter is 0.05 μm~500 μm.
5. lithium slurry battery anode slice as claimed in claim 1, it is characterised in that：The positive-active material of the positive-active layer
Expect to close for LiFePO4, lithium manganese phosphate, lithium metasilicate, ferric metasilicate lithium, sulphate cpd, sulphur carbon complex, sulphur simple substance, titanium vulcanization
Thing, molybdenum sulfur compound, iron sulphur compound, doped lithium manganese oxide, lithium and cobalt oxides, Li-Ti oxide, lithium-barium oxide, lithium nickel
Mn oxide, lithium nickel cobalt oxides, lithium nickel cobalt aluminum oxide, lithium nickel aluminum oxide, lithium nickel cobalt manganese oxide, lithium iron nickel-manganese-oxygen
One or more in thing.
6. lithium slurry battery anode slice as claimed in claim 1, it is characterised in that：The porous afflux anode layer is that thickness is
0.01 μm~2000 μm of the electron conducting layer with through-hole structure, its through hole porosity are 10%~90%, pore diameter range
0.005mm~2mm；The porous afflux anode layer is metal conducting layer, and the metal conducting layer is that wire netting or wire are compiled
Knitmesh, mesh are square, rhombus, rectangle or polygon；Or the metal conducting layer is the porous bubble with loose structure
Foam metal level；Or the metal conducting layer is that metallic plate or metal foil form through mechanical stamping or chemical attack, the metal
The material of conductive layer is aluminium, alloy aluminum, stainless steel, silver, tin or titanium；Or the porous afflux anode layer is electric conduction of carbon fiber
The conductive fabric that cloth, wire mix with organic fiber silk, the material of the wire is copper, nickel or titanium；Or the porous collection
Stream anode layer is that surface coats conductive coating or is coated with the metal conducting layer, conductive fabric, porous organic material or micro- of metallic film
Hole inorganic non-metallic material, the porous organic material include natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and gathered
Tetrafluoroethene, the microporous inorganic nonmetallic materials include glass fibre non-woven, ceramic fiber paper, the conductive coating or gold
The material for belonging to film is aluminium, alloy aluminum, stainless steel or silver；Or the porous afflux anode layer is metal conducting layer, conduction
Cloth, porous organic material, inorganic non-metallic material, surface coating conductive coating are coated with the metal conducting layer of metallic film, led
Electric cloth, inorganic non-metallic material, the composite bed of porous organic material and polymer dielectric, the polymer dielectric are polymerization
The gel polymer electrolyte composite of thing matrix, liquid organic plasticizers and the compound composition of lithium salts three parts；It is or described
Porous afflux anode layer is by above-mentioned any assembly that two or more are formed.
7. lithium slurry battery anode slice as claimed in claim 6, it is characterised in that：At the grid of the porous afflux anode layer
By vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, machinery press-in, printing or inkjet printing in one kind or
Several ways compound interface improves layer；The material of the interface improvement layer includes conductive agent and binding agent, binding agent and conductive agent
Mass ratio be 0.5~20：99.5~80, or the interface improvement layer only includes conductive agent.
8. lithium slurry battery anode slice as claimed in claim 6, it is characterised in that：The porous afflux anode layer also includes anti-
Porous-Organic layer is leaked, the leakproof Porous-Organic layer is compound in the one side or both sides of the porous afflux anode layer, or works as institute
The leakproof Porous-Organic layer can be arranged at porous afflux positive pole when stating porous anode current collector layer with double-deck or sandwich construction
Among layer；The conductive fabric that the material of the leakproof Porous-Organic layer is electric conduction of carbon fiber cloth, wire mixes with organic fiber silk,
Or pore screen cloth, glass fiber non-woven for natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE)
Cloth or ceramic fiber paper；Or the leakproof Porous-Organic layer is conductive fabric, pore screen cloth, glass fibre non-woven, ceramics
Fibrous paper surface coats conductive coating or is coated with metallic film so that leakproof Porous-Organic layer and porous afflux anode layer rise jointly
To the effect of afflux, the average pore size and thickness of the leakproof Porous-Organic layer are respectively less than the porous afflux anode layer, described
The aperture of leakproof Porous-Organic layer be 10 μm~800 μm, 0.01 μm~1000 μm of thickness, its through hole porosity be 10%~
90%.
9. the lithium slurry battery anode slice as described in claim 3,4 or 7, it is characterised in that：The conductive agent is carbon black, section
Qin is black, the one or more in graphene, CNT, carbon fiber, amorphous carbon or metallic conduction particle；The binding agent is
Potential window is wide and aligns negative active core-shell material and the polymeric material of electrolyte stabilization, and the polymeric material is polychlorostyrene second
It is alkene, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyimides, polyethers nitrile, poly-
Methyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene, poly- second
Alkynes, polypyrrole and its derivative, polythiophene and its derivative, Polyaniline and its derivative, poly-phenylene vinylene (ppv) and its derivative,
Gather to the one or more in benzene and its derivative, polyfluorene and its derivative.
A kind of 10. preparation technology of lithium slurry battery anode slice as described in claim 1~9, it is characterised in that positive-active
Layer is among two layers of porous afflux anode layer, and the positive-active layer prepared in the lithium slurry battery anode slice completed contains portion
Point or whole non-adhesive fix positive conductive particle, comprise the following steps：
(1), pre-treatment of raw material：Porous afflux anode layer is sprayed and is cleaned by ultrasonic using cleaning solvent, and is dried standby
With；Required conductive agent, positive electrode active materials, binding agent are dried for standby；Wherein, binding agent drying temperature is less than bonding agent material
Expect 20 DEG C of softening point, drying time is no more than 2h, and conductive agent and positive electrode active materials drying temperature can be dried at 100~250 DEG C
2~4h of time；
(2) positive-active layer slurry, is prepared：According to the positive electrode active materials required for proportioning weighing porous anode material layer, lead
Electric agent and binding agent, three is uniformly mixed to obtain positive-active layer slurry；
(3), it is coated with positive-active layer：The positive-active layer slurry obtained in above-mentioned steps (2) is passed through into the uniform interval of coating machine
The side of porous afflux anode layer is coated on so as to form multiple coating zones；
(4), section turnover：Two neighboring coating zone in step (3) is cut into slices as a unit, the unit after section
From middle doubling, turn into quasi- pole piece, the porous afflux anode layer uncoated one of each quasi- pole piece faces outwardly；
(5), pressing and stoving：Suitably pressurizeed in quasi- pole piece upper and lower surface with clamping plate, be subsequently placed in high temperature oven drying, drying temperature
100~140 DEG C, 2~24h of drying time, the quasi- pole piece after drying naturally cools to room temperature in baking oven, after drying in pole piece
Positive-active layer contains the positive conductive particle that some or all of non-adhesive is fixed；
(6) edge seal：Four sides of quasi- pole piece are encapsulated using ultrasonic bonding machine welding, adding insulating frame by hot pressing obtains just
Pole piece.
11. the preparation technology of lithium slurry battery anode slice as claimed in claim 10, it is characterised in that in the step (1),
After the completion of porous afflux anode layer cleaning, drying, at the grid of porous afflux anode layer by vacuum evaporation, magnetron sputtering, etc.
One or more of mode compound interfaces in ion deposition, spraying, bonding, machinery press-in, printing or inkjet printing improve layer.
12. the preparation technology of lithium slurry battery anode slice as claimed in claim 10, it is characterised in that in the step (1),
After the completion of porous afflux anode layer cleaning, drying, in the one side of porous afflux anode layer or both sides or porous afflux anode layer
Among double-deck or sandwich construction leakproof Porous-Organic layer is compounded with by way of mechanical press, bonding, coating.
13. the preparation technology of lithium slurry battery anode slice as claimed in claim 10, it is characterised in that in the step (2),
The positive-active layer slurry includes the first positive-active layer slurry and the second positive-active layer slurry, wherein the first positive-active
Layer slurry passes through vacuum evaporation, magnetron sputtering, plasma deposition, spraying, bonding, machinery press-in, printing or inkjet printing, coating
In one or more of modes be in close contact with the porous afflux anode layer, the second positive-active layer slurry is steamed by vacuum
One or more side in plating, magnetron sputtering, plasma deposition, spraying, bonding, machinery press-in, printing or inkjet printing, coating
Formula and the first positive-active layer slurry contact.
14. a kind of lithium slurry battery containing the positive plate as described in claim 1-13, including battery core, it is characterised in that：Institute
Stating battery core includes several positive plates and negative plate for alternately placing, and spacing is 0.05 between the positive plate and negative plate
~1mm, the spacing form separate cavities；
The negative plate includes porous afflux negative electrode layer, negative electrode active layer and fixing seal in porous afflux negative electrode layer and negative pole
The insulated enclosure frame of active layer surrounding, wherein negative electrode active layer are between two layers of porous afflux negative electrode layer；The negative electrode active
Layer be metal lithium sheet, or the negative electrode active layer contains the negative conductive particle of some or all of non-adhesive fixation, described
Negative conductive particle for can embedding cathode of lithium active material and conductive agent compound or mixture；It is described can embedding cathode of lithium activity material
Material includes the one or more in graphite, hard carbon, soft carbon, kamash alloy, acieral, lithium titanate or silica-base material.
15. lithium slurry battery as claimed in claim 14, it is characterised in that the battery battery core assembling, dehumidify and vacuumize
After inject electrolyte, electrolyte enters separate cavities, then penetrates into positive-active by the porous afflux anode layer of positive plate
Layer, form part or entirely the positive-active layer of slurry form.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
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| CN201610620726.4A CN107681114B (en) | 2016-08-01 | 2016-08-01 | Positive plate, preparation process and lithium slurry battery containing positive plate |
| PCT/CN2017/075925 WO2017152836A1 (en) | 2016-03-08 | 2017-03-08 | Cell for lithium paste battery, and lithium paste battery module |
| US16/082,838 US10868337B2 (en) | 2016-03-08 | 2017-03-08 | Cell-core for lithium slurry battery, and lithium slurry battery module |
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| CN201610620726.4A CN107681114B (en) | 2016-08-01 | 2016-08-01 | Positive plate, preparation process and lithium slurry battery containing positive plate |
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