CN109216655A - A kind of mutually independent lithium slurry battery system of charge and discharge - Google Patents
A kind of mutually independent lithium slurry battery system of charge and discharge Download PDFInfo
- Publication number
- CN109216655A CN109216655A CN201710550177.2A CN201710550177A CN109216655A CN 109216655 A CN109216655 A CN 109216655A CN 201710550177 A CN201710550177 A CN 201710550177A CN 109216655 A CN109216655 A CN 109216655A
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- CN
- China
- Prior art keywords
- lithium
- chamber
- anode
- sizing agent
- charging
- Prior art date
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- Granted
Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 215
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000002002 slurry Substances 0.000 title claims abstract description 53
- 238000004513 sizing Methods 0.000 claims abstract description 94
- 238000007600 charging Methods 0.000 claims abstract description 86
- 238000000926 separation method Methods 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 30
- 230000008569 process Effects 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000006183 anode active material Substances 0.000 claims abstract description 17
- 210000001787 dendrite Anatomy 0.000 claims abstract description 13
- 239000010410 layer Substances 0.000 claims description 133
- 239000003795 chemical substances by application Substances 0.000 claims description 92
- 229920001971 elastomer Polymers 0.000 claims description 36
- 239000000806 elastomer Substances 0.000 claims description 31
- 239000000463 material Substances 0.000 claims description 30
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- -1 sulfurous acid glycol ester Chemical class 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000012546 transfer Methods 0.000 claims description 20
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- 239000007769 metal material Substances 0.000 claims description 14
- 239000003792 electrolyte Substances 0.000 claims description 9
- 239000012530 fluid Substances 0.000 claims description 9
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- 238000009413 insulation Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
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- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
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- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
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- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 2
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- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 150000003222 pyridines Chemical class 0.000 claims description 2
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- 239000011347 resin Substances 0.000 claims description 2
- 229920002379 silicone rubber Polymers 0.000 claims description 2
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims 1
- 150000001412 amines Chemical group 0.000 claims 1
- 229910052731 fluorine Inorganic materials 0.000 claims 1
- 239000011737 fluorine Substances 0.000 claims 1
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- 238000009831 deintercalation Methods 0.000 abstract 2
- 239000007774 positive electrode material Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 239000006258 conductive agent Substances 0.000 description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 description 10
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 10
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- 239000004744 fabric Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000007773 negative electrode material Substances 0.000 description 7
- 239000011135 tin Substances 0.000 description 7
- 229910052718 tin Inorganic materials 0.000 description 7
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 229910045601 alloy Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229920000049 Carbon (fiber) Polymers 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000004917 carbon fiber Substances 0.000 description 5
- 229910021389 graphene Inorganic materials 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 229920000742 Cotton Polymers 0.000 description 4
- 239000004677 Nylon Substances 0.000 description 4
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- 239000005020 polyethylene terephthalate Substances 0.000 description 4
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 210000005069 ears Anatomy 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229920002319 Poly(methyl acrylate) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 229910003460 diamond Inorganic materials 0.000 description 2
- 239000010432 diamond Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 150000002641 lithium Chemical class 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
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- 229920000570 polyether Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008365 Li-Sn Inorganic materials 0.000 description 1
- 229910008416 Li-Ti Inorganic materials 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- 229910006309 Li—Mg Inorganic materials 0.000 description 1
- 229910006745 Li—Sb Inorganic materials 0.000 description 1
- 229910006759 Li—Sn Inorganic materials 0.000 description 1
- 229910006861 Li—Ti Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- STUKNTHDFYCZOR-UHFFFAOYSA-N [Ba+2].[O-2].[Li+] Chemical compound [Ba+2].[O-2].[Li+] STUKNTHDFYCZOR-UHFFFAOYSA-N 0.000 description 1
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical class [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 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 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- CKFRRHLHAJZIIN-UHFFFAOYSA-N cobalt lithium Chemical compound [Li].[Co] CKFRRHLHAJZIIN-UHFFFAOYSA-N 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000011883 electrode binding agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 description 1
- RSNHXDVSISOZOB-UHFFFAOYSA-N lithium nickel Chemical compound [Li].[Ni] RSNHXDVSISOZOB-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical group 0.000 description 1
- 229910052912 lithium silicate Inorganic materials 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920006124 polyolefin elastomer Polymers 0.000 description 1
- 229920006389 polyphenyl polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical compound [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- 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)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of mutually independent lithium slurry battery systems of charge and discharge, comprising: positive chamber is equipped with anode sizing agent in positive chamber；Charge cathode chamber, is provided with the first anode active material layer；First separation layer is located between charging cathode chamber and positive chamber；Discharge cathode chamber, is provided with the second anode active material layer；Second separation layer is located between electric discharge cathode chamber and positive chamber.Wherein, in battery charging process, lithium ion deintercalation in the intracavitary anode sizing agent of anode is simultaneously embedded into the first intracavitary anode active material layer of charging cathode；In battery discharge procedure, lithium ion deintercalation in intracavitary the second anode active material layer of electric discharge cathode is simultaneously embedded into the intracavitary anode sizing agent of anode.The mutually independent lithium slurry battery system operation operation of the charge and discharge is more flexible, not by the restriction of when and where, and can solve the safety problem that Li dendrite caused by traditional lithium slurry battery punctures separation layer.
Description
Technical field
The present invention relates to energy-storage battery fields, more particularly to a kind of mutually independent lithium slurry battery system of charge and discharge.
Background technique
The new energy technologies such as solar energy, wind energy have many characteristics, such as it is unstable, discontinuous, uncontrollable, energy storage technology be solve
The effective measures of problem above.Electrochemical energy storage technology is using chemical element as energy-accumulating medium, along with storage in charge and discharge process
The chemical reaction process of energy medium.Lithium slurry battery is a kind of novel lithium battery.It is equipped with and leads in the reactor of lithium slurry battery
Plasma-based material, electrocondution slurry contain the conductive particle that certain proportion suspends or precipitates in the electrolytic solution, when battery is by external impact
Or when concussion, since this partially electronically conductive particle is not adhesively fixed, can local motion in the electrolytic solution, formed dynamic
Conductive network.Battery caused by electrocondution slurry in lithium slurry battery can fall off or loosen to avoid traditional electrode material of lithium battery
Capacity declines problem and cycle life attenuation problem, but there are also to be developed in the application of extensive energy storage field.
Currently, lithium slurry battery as other traditional energy-storage batteries, can only carry out charge or discharge in a certain period,
Therefore the working efficiency of battery system and using flexible are restricted.In addition, lithium dendrite growth caused by lithium anode
Also the safety and cycle life problem of battery are influenced whether.In battery charge and discharge process, lithium anode surface grows lithium
Dendrite, when lithium dendrite growth to a certain extent when may penetrate diaphragm, cause safety problem；In addition, Li dendrite is broken
It will form " dead lithium ", cause battery capacity to lose, influence cycle performance of battery.
Summary of the invention
For the problem present on, the present invention provides a kind of mutually independent lithium slurry battery system of charge and discharge, the lithium
Slurry battery system includes that may be disposed at same reactor shell or the intracorporal charging cathode chamber of different reactor shell and discharge negative
Pole chamber, so that the charging process of battery system and discharge process are mutually indepedent.In addition, in charging cathode chamber, first
Settable protective layer between separation layer and the first body containing lithium metal, for preventing lithium dendrite growth in charging process from puncturing diaphragm；
In electric discharge cathode chamber, in the settable elastomer in side of second body containing lithium metal far from the second separation layer, with discharge process
Second body containing lithium metal is constantly promoted to the second separation layer by elastomer, gap increase is avoided to lead by the consumption of middle lithium metal
Polarization resistance is caused to increase.The charge and discharge mutually independent lithium slurry battery system operation operation is more flexible, not by the time and
The restriction in place, and absolute construction design can be carried out for charging cathode chamber and electric discharge cathode chamber, to solve traditional
Li dendrite caused by lithium slurry battery punctures the safety problem of separation layer.
The purpose of the present invention is to achieve the following:
A kind of mutually independent lithium slurry battery system of charge and discharge, the reactor of the lithium slurry battery system includes: anode
Chamber is equipped with anode sizing agent in the anode chamber；Charge cathode chamber, is equipped with the first negative electrode active material in charging cathode chamber
Layer；First separation layer is located between charging cathode chamber and positive chamber；Discharge cathode chamber, is equipped with second in electric discharge cathode chamber
Anode active material layer；And second separation layer, it is located between electric discharge cathode chamber and positive chamber.Wherein, it charged in battery
Cheng Zhong, the lithium ion in the intracavitary anode sizing agent of anode deviate froms and are embedded into the first intracavitary anode active material layer of cathode that charges
In；In battery discharge procedure, the lithium ion in the second intracavitary anode active material layer of electric discharge cathode is deviate from and is embedded into just
In extremely intracavitary anode sizing agent, so that the charging process of lithium slurry battery system and discharge process are mutually indepedent.
First anode active material layer and the second anode active material layer can coat for negative electrode slurry, negative electrode active material
One or more of layer and body containing lithium metal.Wherein, negative electrode slurry is to disperse negative conductive particle in electrolyte, cathode
The thickness of pulp layer can be 0.5mm~10mm.Negative conductive mean particle size can be 0.05 μm~500 μm, and cathode is led
Electric particle is the compound or mixture of negative electrode active material and conductive agent, wherein the mass ratio of negative electrode active material and conductive agent
Preferably 20~98:80~2.Negative electrode active material be can embedding lithium acieral, silicon-base alloy, kamash alloy, lithium titanyl
One of object, lithium Si oxide, metallic lithium powder and graphite are a variety of；Conductive agent can be carbon black, Ketjen black, graphene, carbon
One or more of nanotube, carbon fiber, amorphous carbon, graphene and metallic conduction particle.Wherein, negative electrode active material applies
Coating is that negative conductive particle is coated on to current collector layer, and the overall thickness of coating is 0.05mm~2.5mm, porosity is 10%~
90%, 0.001 μm~10 μm of average pore size scope.Wherein, the material of the body containing lithium metal can be lithium metal or lithium-base alloy.Lithium
Based alloy can be Li-Al, Li-Si, Li-Mg, Li-Sn, Li-Bi, Li-Sb etc., can be the either polynary conjunction of binary, ternary
Gold may include that Mg, Ca, Al, Si, Ge, Sn, Pb, As, Sb, Bi, Pt, Ag, Au, Zn, Cd, Hg etc. can be consolidated with lithium in alloy
Molten and/or addition reaction element, wherein the content of non-elemental lithium is not more than 50%.
Anode sizing agent is to disperse positive conductive particle in electrolyte, the thickness of anode sizing agent layer can for 0.5mm~
10mm.Positive conductive mean particle size can be 0.05 μm~500 μm, and positive conductive particle is positive electrode active materials and conduction
The compound or mixture of agent, wherein the mass ratio of positive electrode active materials and conductive agent is preferably 20~98:80~2.Anode is living
Property material is the compound that can provide lithium ion, including LiFePO4, lithium manganese phosphate, lithium metasilicate, ferric metasilicate lithium, sulfate chemical combination
Object, sulphur carbon complex, sulphur simple substance, titanium sulphur compound, molybdenum sulfur compound, iron sulphur compound, doped lithium manganese oxide, lithium cobalt oxidation
Object, Li-Ti oxide, lithium-barium oxide, Li, Ni, Mn oxide, lithium nickel cobalt oxides, lithium nickel cobalt aluminum oxide, lithium nickel alumina
Object, lithium nickel cobalt manganese oxide, lithium iron Ni, Mn oxide and it is other can one of lithium intercalation compound etc. or a variety of.Conductive agent can
Think one or more of carbon black, graphene, carbon nanotube, carbon fiber, amorphous carbon, metallic conduction particle etc..
Preferably, the first anode active material layer is the first body containing lithium metal and is additionally provided with and prevents in the cathode chamber that charges
Li dendrite punctures the protective layer of the first separation layer, and protective layer is set between the first separation layer and the first body containing lithium metal；Second
Anode active material layer is the second body containing lithium metal and is additionally provided in electric discharge cathode chamber to push the second body containing lithium metal
Against the elastomer of the second separation layer, elastomer be set to the second body containing lithium metal with the second non-contacting side of separation layer.
The thickness of first body containing lithium metal can be 0.5mm~10mm, and the thickness of the second body containing lithium metal can be 0.5mm~10mm.
The thickness of first body containing lithium metal is preferably less than the thickness of the second body containing lithium metal.When battery is charged, anode sizing agent
Positive electrode active materials in lithium ion by the first separation layer be embedded into charging cathode chamber the first body containing lithium metal in, charge
Positive electrode active materials, which are in, afterwards has taken off lithium state, can repeatedly carry out such as surface polishing after charging to the first body containing lithium metal
Processing is to complete the maintenance regeneration of system or can carry out material recovery regeneration to the first body containing lithium metal.When battery carries out
When electric discharge, the lithium ion in the second body containing lithium metal of cathode chamber that discharges is embedded into the anode of anode sizing agent by the second separation layer
In active material, positive electrode active materials are in embedding lithium state after electric discharge, and the second body containing lithium metal constantly consumes after multiple discharge,
But the second body containing lithium metal is contacted with the second separation layer always under the promotion of elastomer, and the second body containing lithium metal is depleted to centainly
The maintenance that can carry out system after degree by replacement the second body containing lithium metal of supplement regenerates.
The safety of battery system can be realized by the protective layer being arranged in charging cathode chamber.The protective layer can be
Separate cavities full of electrolyte, the height of separate cavities for example can be 0.05mm~1mm.In addition, in the electrolyte of separate cavities
It can add for improving the stability of body interface containing lithium metal and/or inhibiting the additive of lithium dendrite growth, additive can be
Metal cation more lower than lithium ion reduction potential, the metal cation may include alkali metal ion Cs+, Rb+ etc.；Or
Person, additive can be organic additive, the organic additive may include small molecule class additive or polymerization species additive,
Small molecule class additive may include fluorinated ethylene carbonate (FEC), vinylene carbonate (VC) and sulfurous acid glycol ester
(ES) etc., polymerization species additive may include polyvinylpyrrolidone (PVP), polyacrylonitrile (PAN) and polyethylene glycol oxide
(PEO) etc.；Alternatively, additive can be ionic liquid, the ion in the ionic liquid may include imidazoles, pyroles, pyrrole
The anion such as the cation such as pyridine class, quaternary ammonium and hexafluorophosphoric acid, fluoboric acid, sulfonic acid and its derivative.Alternatively, the protective layer can be with
For porous insulation separation layer, the thickness of porous insulation separation layer for example can be 0.005mm~1mm, porous insulation separation layer
Material can be the nonconducting polymer material of electronics and/or the nonconducting inorganic non-metallic material of electronics.Electronics is nonconducting
Polymer material can be one or more of polyethylene, polypropylene, Kynoar etc., the nonconducting inorganic non-gold of electronics
Belonging to material can be one or more of glass fibre non-woven, non-woven fabrics of synthetic fiber, ceramic fiber paper etc..
In order to avoid increasing institute by the gap between electric discharge cathode intracavitary the second body containing lithium metal and the second separation layer
Caused polarization resistance increases, and is provided with elastomer electric discharge cathode is intracavitary, elastomer be located at the second body containing lithium metal not with
The side of second separation layer contact.Elastomer is in compressive state and the gradually progress with discharge process before battery discharge
And gradually spring back, by elastomer to the second body containing lithium metal apply pressure so as to avoid the second body containing lithium metal and second every
Gap is generated between absciss layer.Elastomer has good elasticity, and distance change may range from 0.5mm~100mm.Elastomer
It can be the elastic support made of elastic material, elastic support includes thermoplastic elastomer (TPE) and thermo-setting elastomer, heat
Thermoplastic elastic may include polyolefin, modified polyurethane, polystyrene and polyamide etc., and thermo-setting elastomer may include fourth
Benzene rubber, butadiene rubber, isoprene rubber, ethylene propylene diene rubber, butyl rubber, neoprene, fluorubber and corrosion-resistant silicon rubber
Deng.Alternatively, elastomer can be spring, the material of spring can be the metal material or nonmetallic materials of electrolyte resistance corrosion,
Metal material may include alloy material made of stainless steel, copper, nickel, titanium etc. and the above metal material, and nonmetallic materials can be with
Including resin, rubber and plastics etc..
Anode collection layer is equipped in positive chamber, anode collection layer can be for a thickness of 1 μm~2000 μm, preferably 0.05
μm~1000 μm of electron conducting layer.Anode collection layer is preferably the electron conducting layer with through-hole structure, and aperture can be
0.01 μm~2000 μm, preferably 10 μm~1000 μm, through-hole porosity can be 10%~90%.Anode collection layer can be
Conductive metal layer, conductive metal layer are metal mesh, woven wire cloth, expanded metal or multicellular metal foil, and mesh can be
Rectangular, diamond shape, rectangle or polygon etc.；Alternatively, conductive metal layer is the foam metal net with through-hole structure；Alternatively, leading
Metal layer is metal plate or metal foil, and the material of conductive metal layer can be stainless steel, aluminium or silver etc..Alternatively, anode collection
The conductive fabric that layer can mix for electric conduction of carbon fiber cloth, wire with organic fiber silk, the material of wire can be aluminium, alloy
Aluminium, stainless steel or silver etc., organic fiber silk may include natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoro
One or more of ethylene etc..Alternatively, anode collection layer is led for the metal that surface coats conductive coating or is coated with metallic film
Electric layer, conductive fabric, inorganic non-metallic material, porous organic material, conductive coating be conductive agent and binder mixture or
Conductive coating is the mixture of conductive agent, positive electrode active materials and binder, and mixed mode is bonding, spraying, vapor deposition or machine
Tool pressing, porous organic material includes natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE), inorganic non-
Metal material includes glass fibre non-woven, ceramic fiber paper, and conductive agent is carbon black, Ketjen black, graphene, carbon nanotube, carbon
One or more of fiber, amorphous carbon, metallic conduction particle and metallic conduction fiber, metallic conduction particle or metal are led
The material of electric fiber can be aluminium, stainless steel or silver etc., and binder can be polyvinyl chloride, polyethylene, polypropylene, polyphenyl second
Alkene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar,
One or more of polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose and improved polyalkene.Alternatively, anode collection
Fluid layer is two or more above-mentioned any composed assemblys.Positive pole ear is connected on anode collection layer.
Negative pole currect collecting layer can be equipped in charging cathode chamber and electric discharge cathode chamber, negative pole currect collecting layer can be for a thickness of 1 μm
~2000 μm, preferably 0.05 μm~1000 μm of electron conducting layer, negative pole currect collecting layer are preferably the electronics with through-hole structure
Conductive layer, aperture can be 0.01 μm~2000 μm, preferably 10 μm~1000 μm, through-hole porosity can for 10%~
90%.Negative pole currect collecting layer can be conductive metal layer, and conductive metal layer can be metal mesh, woven wire cloth, porous metals
Plate or multicellular metal foil, mesh can be rectangular, diamond shape, rectangle or polygon etc.；Alternatively, conductive metal layer can for
The porous foam metal layer of porous structure；Alternatively, conductive metal layer can be metal plate or metal foil, the material of conductive metal layer
It can be stainless steel, nickel, titanium, tin, tin-coated copper or nickel-clad copper etc..Alternatively, negative pole currect collecting layer can be electric conduction of carbon fiber cloth, metal
The conductive fabric that silk is mixed with organic fiber silk, the material of wire can be stainless steel, nickel, titanium, tin, tin-coated copper or nickel-clad copper
Deng；Organic fiber silk includes one of natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE) or several
Kind.Alternatively, negative pole currect collecting layer can coat conductive coating for surface or be coated with the metal conducting layer, conductive fabric, nothing of metallic film
Machine nonmetallic materials, porous organic material, conductive coating can be that conductive agent and binder or conductive agent, cathode can intercalation materials of li ions
With the compound of binder, compound mode can be bonding, spraying, vapor deposition or mechanical press etc., and porous organic material can be with
Including natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE) etc., inorganic non-metallic material may include
Glass fibre non-woven and ceramic fiber paper etc., the material of conductive film can be stainless steel, nickel, titanium, tin, tin-coated copper or nickel plating
Copper etc., conductive agent can be carbon black, Ketjen black, graphene, carbon nanotube, carbon fiber, amorphous carbon, metallic conduction particle and gold
Belong to one or more of conductive fiber, the material of metallic conduction particle or metallic conduction fiber can for aluminium, stainless steel or
Silver etc., binder can be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, gather
Amide, polyimides, polyethers nitrile, polymethyl acrylate, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, carboxymethyl
One or more of sodium cellulosate and improved polyalkene.Alternatively, negative pole currect collecting layer can be above-mentioned any two or more of
Combination.Negative lug can connect in negative pole currect collecting layer and/or body containing lithium metal.
The material of separation layer can be the nonconducting porous polymer material of electronics；Alternatively, the material of separation layer can be
The nonconducting inorganic non-metallic material of electronics and the compound porous material of organic polymer；Alternatively, the material of separation layer can be
The gel polymer electrolyte of the nonconducting polymeric matrix of electronics, liquid organic plasticizers and the compound composition of lithium salts three parts is multiple
Condensation material；Alternatively, the material of separation layer can be in the hole of the nonconducting porous polymer material of electronics or inorganic non-
The electrolyte or polymeric colloid of ionic conduction are impregnated in the hole of metal material and the compound porous material of organic polymer
Material, etc..
Positive chamber, charging cathode chamber and the electric discharge cathode chamber of lithium slurry battery system can be set in same reactor shell
Interior, positive chamber is located between charging cathode chamber and electric discharge cathode chamber.In this case, complete between positive chamber and charging cathode chamber
At the charging process of battery, the discharge process of battery is completed between positive chamber and electric discharge cathode chamber.It charging process and discharged
The same positive chamber of Cheng Gongyong, but use different cathode chambers.Because using different cathode chambers, so charging cathode chamber and electric discharge
The intracavitary negative electrode active material of cathode and structure can not be affected one another, independently of each other.It, will just when battery charging
The positive pole ear that pole chamber is connected is electrically connected to the cathode of power supply, and the negative lug that cathode chamber is connected that will charge is electrically connected to electricity
The anode in source；When the cell is discharged, the positive pole ear that positive chamber is connected is electrically connected to the anode of load, by the cathode chamber that discharges
The negative lug connected is electrically connected to the cathode of load.By this lithium slurry battery system, for charging cathode chamber and
Electric discharge cathode chamber carries out the security performance that may insure system in the case where structure design, and the structure of the battery system respectively
It is compact, and also avoid driving equipment additionally required due to electrode slurry flowing and reduce the energy consumption of system.
In addition, charging process and discharge process can be completely independent by lithium slurry battery system according to the present invention.Specifically
Say that the positive chamber of setting charging and charging cathode chamber, are arranged in discharge reactor shell and discharge in charging reaction device shell in ground
Positive chamber and electric discharge cathode chamber.Wherein, charge positive chamber to accommodate the anode sizing agent of embedding lithium and discharge positive chamber to
Accommodating has taken off the anode sizing agent of lithium.In this case, complete in the charging reaction device for being equipped with charge positive chamber and charging cathode chamber
It charges at battery, and completes battery discharge being equipped in the discharge reactor for discharging positive chamber and electric discharge cathode chamber, charging reaction
Device is mutually indepedent with discharge reactor, and charging process can not be limited with discharge process by when and where, while or non-concurrent
It carries out, is carried out with ground or strange land.This lithium slurry battery system not only may insure battery system safety, but also have non-
Often big operation operational flexibility.The positive chamber that charges can be directly connected to by pipeline with the positive intracavitary anode sizing agent of electric discharge or
Person realizes the strange land transport of anode sizing agent by independent storage device.
Wherein, it can be equipped with the first transfer pipeline and the second transfer pipeline between the positive chamber of charging and the positive chamber that discharges,
First transfer pipeline is the anode sizing agent for having taken off lithium in the positive chamber that charges to be delivered in the positive chamber of electric discharge, the second delivery pipe
Road is the anode sizing agent of the embedding lithium in the positive chamber that discharges to be delivered in the positive chamber of charging.First transfer pipeline and second defeated
Send pipeline can with charge positive chamber and electric discharge anode chamber be fixedly connected or the first transfer pipeline and the second transfer pipeline can be with
It realizes by interface and the positive chamber of charging and the positive chamber that discharges and connects and disconnect.In addition, can be equipped in the first transfer pipeline
First anode sizing agent storage device, the first anode sizing agent storage device have taken off the anode slurry of lithium to be stored in the positive chamber that charges
Material, and in the second transfer pipeline can be equipped with the second anode sizing agent storage device, the second anode sizing agent storage device to
The anode sizing agent of embedding lithium is stored in the positive chamber that discharges.It is stored by the first anode sizing agent storage device and the second anode sizing agent
Device, has taken off lithium or the anode sizing agent of embedding lithium can store in the storage device, without being directly entered in reactor, in this way
Ongoing reaction process in charging reaction device or discharge reactor may not necessarily be influenced, so that charging process and electric discharge
Process is independent of one another, will not influence each other.
Wherein, lithium slurry battery system may include de- lithium anode sizing agent storage device and embedding lithium anode sizing agent storage
Device, having taken off lithium anode sizing agent storage device can be in fluid communication by interface and the positive chamber that charges or disconnect and pass through driving
The anode sizing agent for having taken off lithium in the positive chamber that charges can be delivered to by device have been taken off in lithium anode sizing agent storage device, and
De- lithium anode sizing agent storage device can be in fluid communication by interface and the positive chamber that discharges or disconnect and pass through driving device energy
It is enough that the anode sizing agent for having taken off lithium taken off in lithium anode sizing agent storage device is delivered in the positive chamber of electric discharge；Embedding lithium anode slurry
Expect that storage device can be in fluid communication by interface and the positive chamber that discharges or disconnect and can will discharge just by driving device
The anode sizing agent of embedding lithium in the chamber of pole is delivered in embedding lithium anode sizing agent storage device, and embedding lithium anode sizing agent storage
Device can be in fluid communication by interface and the positive chamber that charges or disconnect and can be starched embedding lithium anode by driving device
The anode sizing agent of embedding lithium in material storage device is delivered in the positive chamber of charging.The storage of lithium anode sizing agent has been taken off by independent
The charging and discharging for carrying out lithium slurry battery respectively in strange land may be implemented in device and embedding lithium anode sizing agent storage device.
Present invention has an advantage that
1) flexibility: charging reaction device and the mutually independent structure design of discharge reactor make battery have higher use
Flexibility.
2) energy density: the body containing lithium metal for selecting such as lithium metal is cathode, is capable of providing higher energy density.
3) it safety: is set in the charging reaction device reaction characteristics progress structure different with cathode is directed in discharger respectively
Meter, avoids lithium dendrite growth bring safety issue.
Detailed description of the invention
Fig. 1 is the schematic diagram according to the lithium slurry battery system of first embodiment of the invention；
Fig. 2 is the schematic diagram according to the lithium slurry battery system of second embodiment of the invention；
Fig. 3 is the schematic diagram according to the lithium slurry battery system of third embodiment of the invention.
Reference signs list
1-reactor shell
101-charging reaction device shells
102-discharge reactor shells
2-positive chambers
The positive chamber of 201-chargings
The positive chamber of 202-electric discharges
3-anode collection layers
301-the first anode collection layer
302-the second anode collection layer
4-positive pole ears
401-the first positive pole ear
402-the second positive pole ear
501-charging cathode chambers
502-electric discharge cathode chambers
601-the first negative pole currect collecting layer
602-the second negative pole currect collecting layer
701-the first body containing lithium metal
702-the second body containing lithium metal
801-the first negative lug
802-the second negative lug
901-the first separation layer
902-the second separation layer
10-protective layers
11-elastomers
1201-the first transfer pipeline
1202-the second transfer pipeline
1301-the first anode sizing agent storage device
1302-the second anode sizing agent storage device
1401-charging reaction device interfaces
1402-discharge reactor interfaces
1501-have taken off lithium anode sizing agent storage device
1502-embedding lithium anode sizing agent storage devices
Specific embodiment
Below in conjunction with attached drawing, by embodiment, the present invention will be further described.
Fig. 1 is the schematic diagram according to the lithium slurry battery system of first embodiment of the invention.Lithium slurry battery system packet
It includes: reactor shell 1, positive chamber 2, anode collection layer 3, positive pole ear 4, charging cathode chamber 501, electric discharge cathode chamber 502, first
Body containing lithium metal 701, the first negative lug 801, the first separation layer 901, protective layer 10, the second body containing lithium metal 702, second are negative
Pole tab 802, the second separation layer 902 and elastomer 11.Wherein, positive chamber 2 is located at the middle part in reactor shell 1, positive chamber 2
Separated with charging cathode chamber 501 by the first separation layer 901, positive chamber 2 passes through the second separation layer 902 with electric discharge cathode chamber 502
Separate.Anode sizing agent and anode collection layer 3 are provided in positive chamber 2, positive pole ear 4 is electrically connected to anode collection layer 3.It is filling
The first body containing lithium metal 701 and protective layer 10 are provided in electric cathode chamber 501, protective layer 10 is the separate cavities full of electrolyte,
The height h of separate cavities is 0.5mm, the first body containing lithium metal 701 with a thickness of 1.5mm, the first negative lug 801 is electrically connected to the
One body containing lithium metal 701.It is provided with the second body containing lithium metal 702 and elastomer 11 in electric discharge cathode chamber 502, elastomer 11 is
Original state be squeezed state rubber, the second body containing lithium metal 702 with a thickness of 50mm, the second negative lug 802 is electrically connected to
Second body containing lithium metal 702.
In battery charging process, positive pole ear 4 is electrically connected to the cathode of power supply, and the first negative lug 801 is electrically connected to
The anode of power supply, the lithium ion in the positive electrode active materials of anode sizing agent are embedded into the first body containing lithium metal 701, protective layer 10
The first separation layer 901 can be punctured to avoid the Li dendrite generated on the first body containing lithium metal 701, the positive electrode active materials after charging
In having taken off lithium state.In battery discharge procedure, positive pole ear 4 is electrically connected to the anode of load, 802 electricity of the second negative lug
It is connected to the cathode of load, the lithium ion in the second body containing lithium metal 702 is embedded into the positive electrode active materials of anode sizing agent, bullet
Property body 11 can with the thickness of the second body containing lithium metal 702 be thinned gradually spring back and continue push the second body containing lithium metal 702
Against the second separation layer 902, the positive electrode active materials after electric discharge are in embedding lithium state.
Fig. 2 is the schematic diagram according to the lithium slurry battery system of second embodiment of the invention.Lithium slurry battery system packet
It includes: charging reaction device shell 101, the positive chamber 201 that charges, the first anode collection layer 301, the first positive pole ear 401, charging cathode
Chamber 501, the first negative pole currect collecting layer 601, the first body containing lithium metal 701, the first negative lug 801, the first separation layer 901, protection
Layer 10, discharge reactor shell 102, the positive chamber 202 that discharges, the second anode collection layer 302, the second positive pole ear 402, electric discharge are negative
Pole chamber 502, the second negative pole currect collecting layer 602, the second body containing lithium metal 702, the second negative lug 802, the second separation layer 902, bullet
Property body 11, the first transfer pipeline 1201, the second transfer pipeline 1202, the first anode sizing agent storage device 1301 and the second anode slurry
Expect storage device 1302.Wherein, the positive chamber 201 that charges is set in charging reaction device shell 101 and leads to charging cathode chamber 501
The separation of the first separation layer 901 is crossed, is provided with the anode sizing agent of embedding lithium and the first anode collection layer in the positive chamber 201 that charges
301, the first positive pole ear 401 is electrically connected to the first anode collection layer 301, and first is provided in charging cathode chamber 501 containing lithium
Metallic object 701 and protective layer 10, protective layer 10 be 1mm thickness porous insulation separation layer, the first body containing lithium metal 701 with a thickness of
0.5mm, the first negative lug 801 are electrically connected to the first negative pole currect collecting layer 601.The positive chamber 202 of electric discharge and electric discharge cathode chamber 502 are set
It is placed in discharge reactor shell 102 and is separated by the second separation layer 902, be provided in the positive chamber 202 that discharges and taken off lithium
Anode sizing agent and the second anode collection layer 302, the second positive pole ear 402 is electrically connected to the second anode collection layer 302, discharging
The second body containing lithium metal 702 and elastomer 11 are provided in cathode chamber 502, elastomer 11 is that original state is the stainless of squeezed state
Steel spring, the second body containing lithium metal 702 with a thickness of 80mm, the second negative lug 802 is electrically connected to the second negative pole currect collecting layer
602。
In charging reaction device, the first positive pole ear 401 is electrically connected to the cathode of power supply, and the first negative lug 801 is electrically connected
It is connected to the anode of power supply, the lithium ion in the positive electrode active materials of embedding lithium anode sizing agent is embedded into the first body containing lithium metal 701
In, the positive electrode active materials after charging, which are in, has taken off lithium state.It is defeated via the first transfer pipeline 1201 that lithium anode sizing agent will have been taken off
It send to the first anode sizing agent storage device 1301, and is delivered to the positive chamber 202 of electric discharge in turn.In discharge reactor, second just
Pole tab 402 is electrically connected to the anode of load, and the second negative lug 802 is electrically connected to the cathode of load, the second body containing lithium metal
Lithium ion in 702 is embedded into the positive electrode active materials for having taken off lithium anode sizing agent, and the positive electrode active materials after electric discharge are in
Embedding lithium state.Embedding lithium anode sizing agent is delivered to the second anode sizing agent storage device 1302 via the second transfer pipeline 1202,
And it is delivered to the positive chamber 201 of charging in turn.
Fig. 3 is the schematic diagram according to the lithium slurry battery system of third embodiment of the invention.Lithium slurry battery system packet
It includes: charging reaction device shell 101, the positive chamber 201 that charges, the first anode collection layer 301, the first positive pole ear 401, charging cathode
Chamber 501, the first negative pole currect collecting layer 601, the first body containing lithium metal 701, the first negative lug 801, the first separation layer 901, protection
Layer 10, charging reaction device interface 1401, discharge reactor shell 102, the positive chamber 202 that discharges, the second anode collection layer 302, the
Two positive pole ears 402, electric discharge cathode chamber 502, the second negative pole currect collecting layer 602, the second body containing lithium metal 702, the second negative lug
802, the second separation layer 902, elastomer 11, discharge reactor interface 1402, taken off lithium anode sizing agent storage device 1501 and
Embedding lithium anode sizing agent storage device 1502.Wherein, the positive chamber 201 of charging and charging cathode chamber 501 are set to charging reaction device shell
Separate in body 101 and by the first separation layer 901, is provided with the anode sizing agent of embedding lithium and first in the positive chamber 201 that charges
Anode collection layer 301, the first positive pole ear 401 are electrically connected to the first anode collection layer 301, are arranged in charging cathode chamber 501
There are the first body containing lithium metal 701 and protective layer 10, protective layer 10 is the separate cavities that height is 0.1mm, is full of electrolysis in separate cavities
Liquid is simultaneously added with alkali metal ion Cs+ in the electrolytic solution, the first body containing lithium metal with a thickness of 2mm, 801 electricity of the first negative lug
It is connected to the first negative pole currect collecting layer 601.The positive chamber 202 of electric discharge and electric discharge cathode chamber 502 are set in discharge reactor shell 102
And separated by the second separation layer 902, the anode sizing agent and the second anode collection for having taken off lithium are provided in the positive chamber 202 that discharges
Layer 302, the second positive pole ear 402 is electrically connected to the second anode collection layer 302, is provided with second in electric discharge cathode chamber 502 and contains
Lithium metal body 702 and elastomer 11, elastomer 11 are the polyolefin elastomer that original state is squeezed state, the second body containing lithium metal
702 with a thickness of 50mm, the second negative lug 802 is electrically connected to the second negative pole currect collecting layer 602.
In charging reaction device, the first positive pole ear 401 is electrically connected to the cathode of power supply, and the first negative lug 801 is electrically connected
It is connected to the anode of power supply, the lithium ion in the positive electrode active materials of embedding lithium anode sizing agent is embedded into the first body containing lithium metal,
Positive electrode active materials after charging, which are in, has taken off lithium state.The interface and charging that have taken off lithium anode sizing agent storage device 1501 is anti-
It answers device interface 1401 to dock, lithium anode sizing agent will have been taken off and be delivered to has taken off in lithium anode sizing agent storage device 1501, will connect later
Mouth is disconnected and is sealed.Be stored with taken off the interface for having taken off lithium anode sizing agent storage device 1501 of lithium anode sizing agent can be anti-with electric discharge
It answers device interface 1402 to dock, is delivered in the positive chamber 202 of electric discharge so that lithium anode sizing agent will have been taken off.In discharge reactor, the
Two positive pole ears 402 are electrically connected to the anode of load, and the second negative lug 802 is electrically connected to the cathode of load, and second containing lithium gold
The lithium ion belonged in body 702 is embedded into the positive electrode active materials for having taken off lithium anode sizing agent, at the positive electrode active materials after electric discharge
In embedding lithium state.The interface of embedding lithium anode sizing agent storage device 1502 is docked with discharge reactor interface 1402, it will
Embedding lithium anode sizing agent is delivered in embedding lithium anode sizing agent storage device 1502, and interface is disconnected and sealed later.It is stored with
The interface of the embedding lithium anode sizing agent storage device 1502 of embedding lithium anode sizing agent can be docked with charging reaction device interface 1401, thus
Embedding lithium anode sizing agent is delivered in the positive chamber 201 of charging.
The specific embodiment of the invention is not intended to limit the invention.Anyone skilled in the art is 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 equivalent example modified to equivalent change.Therefore, all without departing from the technology of the present invention side
The content of case, any simple modifications, equivalents, and modifications made to the above embodiment according to the technical essence of the invention,
It still falls within the scope of protection of the technical scheme of the present invention.
Claims (11)
1. a kind of mutually independent lithium slurry battery system of charge and discharge, which is characterized in that the reaction of the lithium slurry battery system
Device includes: positive chamber, is equipped with anode sizing agent in the positive chamber；Charge cathode chamber, is equipped in the charging cathode chamber
First anode active material layer；First separation layer, first separation layer be located at the charging cathode chamber and the positive chamber it
Between；Discharge cathode chamber, and the second anode active material layer is equipped in the electric discharge cathode chamber；Second separation layer, described second every
Absciss layer is located between the electric discharge cathode chamber and the positive chamber, wherein in battery charging process, the anode is intracavitary just
Lithium ion in the slurry of pole is deviate from and is embedded into the first intracavitary anode active material layer of the charging cathode, in battery discharge
In the process, the lithium ion in intracavitary the second anode active material layer of the electric discharge cathode is deviate from and to be embedded into the anode intracavitary
Anode sizing agent in so that the charging process of lithium slurry battery system and discharge process are mutually indepedent.
2. lithium slurry battery system according to claim 1, wherein first anode active material layer is first containing lithium
Metallic object and the protective layer for preventing Li dendrite from puncturing first separation layer, the guarantor are additionally provided in the charging cathode chamber
Sheath is set between first separation layer and first body containing lithium metal；Second anode active material layer is second
It body containing lithium metal and is additionally provided in the electric discharge cathode chamber to push second body containing lithium metal against described second
The elastomer of separation layer, the elastomer are being set to second body containing lithium metal with second separation layer non-contacting one
Side.
3. lithium slurry battery system according to claim 2, wherein the anode chamber, the charging cathode chamber and described
Electric discharge cathode chamber is set in same reactor enclosure body, and the anode chamber is located at the charging cathode chamber and the electric discharge cathode chamber
Between.
4. lithium slurry battery system according to claim 2, wherein the positive chamber includes the positive chamber of charging and discharges just
Pole chamber, the positive chamber of the charging is to accommodate the anode sizing agent of embedding lithium and electric discharge anode chamber has taken off lithium to accommodate
Anode sizing agent, the positive chamber of the charging and the charging cathode chamber are set in charging reaction device shell, the positive chamber of the electric discharge
It is set in discharge reactor shell with the electric discharge cathode chamber.
5. lithium slurry battery system according to any one of claim 2 to 4, wherein the protective layer is full of electrolysis
The separate cavities of liquid, the height of the separate cavities are 0.05mm~1mm；Alternatively,
The protective layer be porous insulation separation layer, the porous insulation separation layer with a thickness of 0.005mm~1mm, it is described more
The material of hole dielectric isolation layer is the nonconducting polymer material of electronics and/or the nonconducting inorganic non-metallic material of electronics.
6. lithium slurry battery system according to claim 5, wherein addition is for changing in the electrolyte of the separate cavities
The kind stability of body interface containing lithium metal and/or the additive for inhibiting lithium dendrite growth, the additive are to restore electricity than lithium ion
The lower metal cation in position, the metal cation includes alkali metal ion Cs+, Rb+；Alternatively, the additive is organic
Additive, the organic additive include small molecule class additive or polymerization species additive, the small molecule class additive packet
Fluorinated ethylene carbonate, vinylene carbonate and sulfurous acid glycol ester are included, the polymerization species additive includes polyvinyl
Pyrrolidones, polyacrylonitrile and polyethylene glycol oxide；Alternatively, the additive is ionic liquid, the ion in the ionic liquid
Including imidazoles, pyroles, pyridines, quaternary amine cationoid and hexafluorophosphoric acid, fluoboric acid, sulfonic acid and its derivative anion.
7. lithium slurry battery system according to claim 5, wherein the polymer material be polyethylene, polypropylene and
One or more of Kynoar, the inorganic non-metallic material be glass fibre non-woven, non-woven fabrics of synthetic fiber and
One or more of ceramic fiber paper.
8. lithium slurry battery system according to any one of claim 2 to 4, wherein the elastomer is in battery discharge
It is in compressive state before and is gradually sprung back with the gradually progress of discharge process, is contained by the elastomer to described second
Lithium metal body applies pressure and generates gap with to avoid between second body containing lithium metal and second separation layer,
Wherein, the elastomer is the elastic support made of elastic material, and the elastic support includes thermoplastic elastic
Body and thermo-setting elastomer, the thermoplastic elastomer (TPE) include polyolefin, modified polyurethane, polystyrene and polyamide, described
Thermo-setting elastomer includes butadiene-styrene rubber, butadiene rubber, isoprene rubber, ethylene propylene diene rubber, butyl rubber, neoprene, fluorine
Rubber and corrosion-resistant silicon rubber；Alternatively, the elastomer is spring, the material of the spring is the metal material of electrolyte resistance corrosion
Material or nonmetallic materials, the metal material include stainless steel, copper, nickel, alloy material made of titanium and the above metal material, institute
Stating nonmetallic materials includes resin, rubber and plastics.
9. lithium slurry battery system according to claim 4, wherein in the positive chamber of the charging and the positive chamber of the electric discharge
Between be equipped with the first transfer pipeline and the second transfer pipeline, first transfer pipeline to by charging anode chamber
The anode sizing agent of de- lithium is delivered in the positive chamber of the electric discharge, and second transfer pipeline is to will be in the electric discharge anode chamber
The anode sizing agent of embedding lithium is delivered in the positive chamber of the charging.
10. lithium slurry battery system according to claim 9, wherein be equipped with first in first transfer pipeline just
Pole slurry storage device, the first anode sizing agent storage device have taken off the anode of lithium to be stored in the positive chamber that charges
Slurry, and the second anode sizing agent storage device is equipped in second transfer pipeline, the second anode sizing agent storage dress
It sets to be stored in the positive chamber that discharges the anode sizing agent of embedding lithium.
11. lithium slurry battery system according to claim 4, wherein the lithium slurry battery system includes taking off lithium just
Pole slurry storage device and embedding lithium anode sizing agent storage device, the anode sizing agent storage device that has disengaged from can pass through interface
It is in fluid communication with the positive chamber that charges or disconnects and lithium can will have been taken off in the positive chamber that charges by driving device
Anode sizing agent be delivered to it is described taken off in lithium anode sizing agent storage device, and described taken off lithium anode sizing agent storage device energy
Enough it is in fluid communication by interface and the positive chamber of the electric discharge or disconnects and lithium anode described can will have been taken off by driving device
The anode sizing agent for having taken off lithium in slurry storage device is delivered in the positive chamber of the electric discharge；
The embedding lithium anode sizing agent storage device can be in fluid communication by interface and the positive chamber of the electric discharge or disconnection and
The anode sizing agent of the embedding lithium in the positive chamber that discharges can be delivered to the embedding lithium anode sizing agent by driving device
In storage device, and the embedding lithium anode sizing agent storage device can be in fluid communication by interface and the positive chamber of the charging
Or disconnect and by driving device can be defeated by the anode sizing agent of the embedding lithium in the embedding lithium anode sizing agent storage device
It send into the positive chamber of the charging.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110518189A (en) * | 2019-10-23 | 2019-11-29 | 湖南省正源储能材料与器件研究所 | It is a kind of at the same realize to positive electrode pre-deoxidation, to the device and method of negative electrode material prelithiation |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
| CN112018370A (en) * | 2019-05-28 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of anode material or metal simple substance capable of being embedded with alkali metal ions |
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| CN1174511C (en) * | 1998-01-28 | 2004-11-03 | 斯奎勒尔控股有限公司 | Rebox flow battery system and cell stack |
| CN100347898C (en) * | 2005-11-18 | 2007-11-07 | 清华大学 | Galvanic pile structure of energy-storing unit of oxidation-reduction fluid flow battery |
| CN105280942B (en) * | 2014-07-01 | 2017-11-28 | 北京好风光储能技术有限公司 | A kind of lithium double flow battery |
| CN105680081B (en) * | 2014-11-17 | 2018-02-09 | 北京好风光储能技术有限公司 | A kind of lithium flow battery discharger |
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| CN112018370A (en) * | 2019-05-28 | 2020-12-01 | 中国科学院宁波材料技术与工程研究所 | Preparation method of anode material or metal simple substance capable of being embedded with alkali metal ions |
| CN112018370B (en) * | 2019-05-28 | 2022-04-15 | 中国科学院宁波材料技术与工程研究所 | Method for preparing metal simple substance |
| CN112216812A (en) * | 2019-07-10 | 2021-01-12 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN112216878A (en) * | 2019-07-10 | 2021-01-12 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN112216878B (en) * | 2019-07-10 | 2021-11-12 | 比亚迪股份有限公司 | Lithium ion battery repeating unit, lithium ion battery, using method of lithium ion battery, battery module and automobile |
| CN110518189A (en) * | 2019-10-23 | 2019-11-29 | 湖南省正源储能材料与器件研究所 | It is a kind of at the same realize to positive electrode pre-deoxidation, to the device and method of negative electrode material prelithiation |
| CN110518189B (en) * | 2019-10-23 | 2020-02-14 | 湖南省正源储能材料与器件研究所 | Device and method for simultaneously realizing pre-deoxidation of anode material and pre-lithiation of cathode material |
| CN110828896A (en) * | 2019-11-21 | 2020-02-21 | 国网上海市电力公司 | Application of metal dendrite inhibiting additive, electrolyte containing additive and battery |
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Address after: No. 1, 1st Floor, Building 4, No. 10, South 3rd Road, Shodu, Wuhou District, Chengdu City, Sichuan Province, 610043 Patentee after: Haofengguang Energy storage (Chengdu) Co.,Ltd. Address before: 1711, 17th floor, building 2, yard 1, Shangdi 10th Street, Haidian District, Beijing 100085 Patentee before: Beijing Hawaga Power Storage Technology Co.,Ltd. |
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Effective date of registration: 20231229 Address after: 1711, 17th floor, building 2, yard 1, Shangdi 10th Street, Haidian District, Beijing 100085 Patentee after: Beijing Hawaga Power Storage Technology Co.,Ltd. Address before: 1711, 17th floor, building 2, yard 1, Shangdi 10th Street, Haidian District, Beijing 100085 Patentee before: Beijing Hawaga Power Storage Technology Co.,Ltd. Patentee before: HEBEI MEIJIANG BATTERY Co.,Ltd. |