CN107681115A - A kind of negative plate of lithium slurry battery - Google Patents
A kind of negative plate of lithium slurry battery Download PDFInfo
- Publication number
- CN107681115A CN107681115A CN201610621508.2A CN201610621508A CN107681115A CN 107681115 A CN107681115 A CN 107681115A CN 201610621508 A CN201610621508 A CN 201610621508A CN 107681115 A CN107681115 A CN 107681115A
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- CN
- China
- Prior art keywords
- lithium
- porous
- afflux
- layer
- embedding
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Links
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 241
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 182
- 239000002002 slurry Substances 0.000 title claims abstract description 98
- 239000000463 material Substances 0.000 claims abstract description 80
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 47
- 230000002687 intercalation Effects 0.000 claims abstract description 35
- 238000009830 intercalation Methods 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 31
- 238000010276 construction Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010410 layer Substances 0.000 claims description 139
- -1 polyethylene Polymers 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- 229910045601 alloy Inorganic materials 0.000 claims description 16
- 239000000956 alloy Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 239000004411 aluminium Substances 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 12
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 12
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 238000007747 plating Methods 0.000 claims description 9
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 239000011231 conductive filler Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 8
- 239000001989 lithium alloy Substances 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 7
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 239000004917 carbon fiber Substances 0.000 claims description 7
- 239000006258 conductive agent Substances 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000835 fiber Substances 0.000 claims description 6
- RRMGGYGDQCMPKP-UHFFFAOYSA-N gold lithium Chemical compound [Li].[Au] RRMGGYGDQCMPKP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003466 welding Methods 0.000 claims description 6
- 229910000733 Li alloy Inorganic materials 0.000 claims description 5
- 239000006229 carbon black Substances 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 239000007769 metal material Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910008416 Li-Ti Inorganic materials 0.000 claims description 4
- 229910006861 Li—Ti Inorganic materials 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 239000004793 Polystyrene Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 239000011230 binding agent Substances 0.000 claims description 4
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000008151 electrolyte solution Substances 0.000 claims description 4
- 239000006260 foam Substances 0.000 claims description 4
- 239000011888 foil Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical group 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 4
- 150000002825 nitriles Chemical class 0.000 claims description 4
- 239000011368 organic material Substances 0.000 claims description 4
- 239000004014 plasticizer Substances 0.000 claims description 4
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920000867 polyelectrolyte Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 4
- 239000004800 polyvinyl chloride Substances 0.000 claims description 4
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 4
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 4
- 239000011135 tin Substances 0.000 claims description 4
- 229910052718 tin Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910001148 Al-Li alloy Inorganic materials 0.000 claims description 3
- FCVHBUFELUXTLR-UHFFFAOYSA-N [Li].[AlH3] Chemical compound [Li].[AlH3] FCVHBUFELUXTLR-UHFFFAOYSA-N 0.000 claims description 3
- 229910003481 amorphous carbon 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
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims description 3
- 238000009413 insulation Methods 0.000 claims description 3
- 150000002500 ions Chemical class 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000000320 mechanical mixture Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229920000728 polyester Polymers 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
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229910000676 Si alloy Inorganic materials 0.000 claims description 2
- 229920004933 Terylene® Polymers 0.000 claims description 2
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 2
- 229920006231 aramid fiber Polymers 0.000 claims description 2
- 239000003575 carbonaceous material Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000003365 glass fiber Substances 0.000 claims description 2
- 238000007731 hot pressing Methods 0.000 claims description 2
- 238000002955 isolation Methods 0.000 claims description 2
- SWAIALBIBWIKKQ-UHFFFAOYSA-N lithium titanium Chemical compound [Li].[Ti] SWAIALBIBWIKKQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052752 metalloid Inorganic materials 0.000 claims description 2
- 150000002738 metalloids Chemical class 0.000 claims description 2
- 239000004745 nonwoven fabric Substances 0.000 claims description 2
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 229920002994 synthetic fiber Polymers 0.000 claims description 2
- 239000012209 synthetic fiber Substances 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims 2
- 239000007921 spray Substances 0.000 claims 2
- 239000010959 steel Substances 0.000 claims 2
- 239000004677 Nylon Substances 0.000 claims 1
- 230000003628 erosive effect Effects 0.000 claims 1
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 229920001778 nylon Polymers 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- 238000007600 charging Methods 0.000 abstract description 14
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 13
- 229910052493 LiFePO4 Inorganic materials 0.000 description 6
- 238000007599 discharging Methods 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- 239000013589 supplement Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- ZVLDJSZFKQJMKD-UHFFFAOYSA-N [Li].[Si] Chemical compound [Li].[Si] ZVLDJSZFKQJMKD-UHFFFAOYSA-N 0.000 description 2
- OCKPCBLVNKHBMX-UHFFFAOYSA-N butylbenzene Chemical compound CCCCC1=CC=CC=C1 OCKPCBLVNKHBMX-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000010405 anode 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
- 210000004027 cell Anatomy 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention provides a kind of negative plate of lithium slurry battery, and the negative plate includes insulated enclosure frame, body containing lithium metal and can embedding lithium afflux structure layer.Wherein, can embedding lithium afflux structure layer, body containing lithium metal and it is another can embedding lithium afflux structure layer form sandwich composite construction, insulated enclosure frame seals the edge of sandwich composite construction, can embedding lithium afflux structure layer material contain be capable of embedding lithium in lithium slurry battery charge and discharge process can intercalation materials of li ions.In negative plate can embedding lithium afflux structure layer can play a part of embedding lithium when charging, avoid lithium from being deposited on the surface of the body containing lithium metal and form Li dendrite, improve the security of battery.Also, body containing lithium metal can also be used as lithium source, consumption of the side reaction to positive pole lithium during the formation of negative pole SEI films and circulating battery is effectively supplemented.In addition, body containing lithium metal and can the common afflux of embedding lithium afflux structure layer make it that catchment effect is uniform, avoid the generation for situations such as generating heat caused by high rate charge-discharge.
Description
Technical field
The invention belongs to electrochemical kinetics cell art, more particularly to a kind of negative plate of lithium slurry battery.
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 phase
Than with a series of advantages such as, voltage high, self discharge small, good cycle and long lifespans higher than energy, increasingly by people
Concern.In recent years, lithium ion battery technology achieves fast development, has started to be applied in electric automobile.
Lithium slurry battery bag contains electrode slice and electrolyte, injects the positive plate of battery and/or negative plate after electrolyte and has been internally formed and has led
Plasma-based material, electrocondution slurry contain the conductive particle that certain proportion suspends or precipitated in the electrolytic solution.When battery by external impact or
It during concussion, because this partially electronically conductive particle is not adhesively fixed, therefore can in the electrolytic solution move, and be formed dynamic conductive
Network.Conductive particle is carbon black, Ketjen black, graphene, CNT, carbon fiber, amorphous carbon or metallic conduction particle etc.
One or more of mixtures in conductive agent, or compound that conductive particle is electrode active material and above-mentioned conductive agent or mix
Thing, compound or mixing mode include Surface coating, bonding or mechanical mixture etc..
In the lithium slurry battery that Chinese invention patent CN201610074921.1 is mentioned, the negative current collector of electronic conduction is close to battery
Separation layer so that battery is in high rate charge-discharge and lithium ion is easily deposited on the surface of negative current collector when overcharging, so as to
Separation layer is pierced through in the presence of " Li dendrite " and causes the danger of internal short-circuit of battery.In addition, Chinese invention patent
CN201510164222.1 proposes a kind of lithium slurry battery that negative current collector is placed in negative reaction intracavitary portion, and the battery is present such as
Lower problem, i.e. cathode size can disappear first and in following cycle along with the generation, destruction and reparation of SEI films, this process
Electrolyte and active lithium are consumed, causes the deterioration of cycle performance of battery.
The content of the invention
For the problem present on, the present invention provides a kind of negative plate of lithium slurry battery.The negative plate includes body containing lithium metal
With can embedding lithium afflux structure layer, this can embedding lithium afflux structure layer can charging when play a part of embedding lithium, avoid lithium from depositing
Li dendrite is formed on the surface of the body containing lithium metal, substantially increases the security of battery.Also, body containing lithium metal can also conduct
Lithium source, effectively supplement consumption of the side reaction to positive pole lithium during the formation of negative pole SEI films and circulating battery.In addition, containing lithium gold
Category body and can the common afflux of embedding lithium afflux structure layer make it that catchment effect is uniform, heating etc. caused by avoiding high rate charge-discharge
The occurrence of.
Technical scheme provided by the invention is as follows：
A kind of negative plate of lithium slurry battery is provided according to the present invention, and the negative plate includes insulated enclosure frame, body containing lithium metal and can
Embedding lithium afflux structure layer, can embedding lithium afflux structure layer, body containing lithium metal and it is another can embedding lithium afflux structure layer form sandwich composite junction
Structure, insulated enclosure frame seal the edge of sandwich composite construction.Can the material of embedding lithium afflux structure layer contain in lithium slurry battery
It is capable of the material of embedding lithium in charge and discharge process, you can intercalation materials of li ions.Preferably, can intercalation materials of li ions be reversible de- in charging process
The material of embedding lithium, including：Can the acieral of embedding lithium, silicon-base alloy, kamash alloy, Li-Ti oxide, lithium Si oxide,
Metallic lithium powder and graphite etc..
Can embedding lithium afflux structure layer may include afflux porous portion, the thickness of afflux porous portion is 0.01 μm~2000 μm, its through hole
Porosity is 30%~98%, and pore diameter range is 10nm~2mm.As described above, can the material of embedding lithium afflux structure layer contain
Be capable of embedding lithium in lithium slurry battery charge and discharge process can intercalation materials of li ions.Specifically, when can embedding lithium afflux structure layer only include collection
Flow porous portion when, afflux porous portion need to contain it is above-mentioned can intercalation materials of li ions.
Can embedding lithium afflux structure layer can also include afflux porous portion and slurry portion simultaneously.According to the porosity of afflux porous portion, hole
The viscosity of slurry in footpath and slurry portion, the slurry that slurry portion can be in or slurry portion adjacent with afflux porous portion can portion
Divide ground or fully penetrate into the hole of afflux porous portion.Wherein, two can embedding lithium afflux structure layer with slurry portion with containing lithium gold
The adjacent mode of category body phase is arranged on the both sides of the body containing lithium metal.So, can the afflux porous portion of embedding lithium afflux structure layer not only can be with
Play a part of embedding lithium, afflux, additionally it is possible to which playing prevents the slurry in slurry portion from being acted on from the leakproof of negative plate seepage.Afflux is more
The thickness of hole portion is 0.01 μm~2000 μm, and through hole porosity is 30%~98%, and pore diameter range is 10nm~2mm, slurry
The thickness in portion is 0~2mm.When can embedding lithium afflux structure layer include afflux porous portion and slurry portion when, afflux porous portion and/or slurry
Material portion contain it is above-mentioned can intercalation materials of li ions, it is preferable that afflux porous portion and slurry portion containing it is above-mentioned can intercalation materials of li ions.Slurry portion can
With including electrolyte and can flow in the electrolytic solution can embedding lithium conductive particle, wherein, can embedding lithium conductive particle account for the slurry
The mass ratio in material portion is 10%~90%, and average grain diameter is 500nm~500 μm.Can embedding lithium conductive particle for can intercalation materials of li ions
With the compound or mixture of conductive agent, wherein, can the mass ratio of intercalation materials of li ions and conductive agent be 0~98：100~2, it is compound or
The mode of mixing includes Surface coating, bonding or mechanical mixture etc., conductive agent be carbon black, Ketjen black, graphene, CNT,
One or more in carbon fiber, amorphous carbon or metallic conduction particle etc..
Afflux porous portion can be single layer structure or be sandwich construction.In other words, afflux porous portion can be porous including one
Layer or multiple porous layers.When afflux porous portion includes a porous layer, the porous layer had both played a part of embedding lithium, played again
The effect of afflux.That is, the material of the porous layer be embedding lithium metal conductive material or be covered with can intercalation materials of li ions conduction material
Material.When afflux porous portion includes multiple porous layers, material, thickness, porosity and the aperture of each porous layer can with identical or
Person can be different, as long as one of porous layer can play a part of embedding lithium and one of porous layer can play afflux
Effect.Multiple porous layers can by welding, spraying, being bonded, the mode such as machinery press-in connects together.With multiple
The advantage of porous layer is, can be by being actually needed the material for specifically adjusting each porous layer, thickness, porosity and aperture.
By can embedding lithium afflux structure layer-body containing lithium metal-can the surrounding of sandwich composite construction that forms of embedding lithium afflux structure layer
Edge is provided with insulated enclosure frame.The insulated enclosure frame is connected to sandwich composite construction by modes such as hot pressing, stickups.Insulated enclosure frame
Play a part of insulation, also, when can embedding lithium afflux structure layer include slurry portion when, insulated enclosure frame also acts as the effect of sealing
To prevent edge seepage of the slurry in slurry portion from sandwich composite construction.The material of insulated enclosure frame is insulation electrolyte resistance
Polymeric material, for example, polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), poly terephthalic acid
Ester, polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butylbenzene rubber
One or more in glue, sodium carboxymethylcellulose and improved polyalkene etc..
The separation layer of electronic isolation ion conducting can be provided with the surface of negative plate.The material of separation layer is that electronics is nonconducting more
Pore polymer material, such as：Polyethylene, polypropylene, Kynoar etc.；Or the material of separation layer is that electronics is non-conductive
Inorganic non-metallic material and organic polymer composite porous material, such as：Glass fibre non-woven, non-woven fabrics of synthetic fiber,
Ceramic fiber paper etc.；Or the material of separation layer is the nonconducting polymeric matrix of electronics, liquid organic plasticizers and lithium salts three
The gel polymer electrolyte composite of the compound composition in part；Or the material of separation layer is nonconducting porous poly- in electronics
In the hole of compound material or ion is impregnated with the hole of inorganic non-metallic material and the composite porous material of organic polymer to lead
The electrolyte or polymeric colloid material of electricity.
The material of the body containing lithium metal is lithium metal or rich lithium alloy.Rich lithium alloy is for example including aluminium lithium alloy, lithium magnesium alloy, lithium silicon
Alloy etc..When can embedding lithium afflux structure layer only include afflux porous portion when, body containing lithium metal can by welding, spraying, being bonded,
The modes such as electrochemical plating, chemical plating or machinery press-in are fixed on afflux porous portion.When can embedding lithium afflux structure layer include afflux it is porous
When portion and slurry portion, by above-mentioned insulated enclosure frame come be fixedly connected can embedding lithium afflux structure layer-body containing lithium metal-can embedding lithium
The sandwich composite construction of afflux structure layer.Wherein, body containing lithium metal can be used as lithium source supplement negative pole SEI films formation and battery
Consumption of the side reaction to positive pole lithium in cyclic process.
Negative plate is provided with negative lug, negative lug can with can embedding lithium afflux structure layer afflux porous portion electrically connect or with containing lithium
Metallic object electrically connects；Or negative lug can with can embedding lithium afflux structure layer afflux porous portion electrically connect and with containing lithium gold
Belong to body electrical connection.That is, can embedding lithium afflux structure layer and body containing lithium metal can play a part of collector.When can be embedding
When lithium afflux structure layer and body containing lithium metal while afflux, catchment effect is uniform, can avoid the hair caused by high rate charge-discharge
The generation of situations such as hot.
Afflux porous portion can be it is porous can embedding lithium metal conductive layer, or can be surface be covered with can intercalation materials of li ions porous, electrically conductive
Layer.
Wherein, when afflux porous portion for it is porous can embedding lithium metal conductive layer when, it is porous can embedding lithium metal conductive layer can be wire netting
Or woven wire cloth, mesh are square, rhombus, rectangle or polygon etc.；Or it is porous can embedding lithium metal conductive layer be
Porous foam metal layer with loose structure；Or it is porous can embedding lithium metal conductive layer be expanded metal or metal foil through machine
Tool punching press or chemical attack form.It is porous can embedding lithium metal conductive layer material for aluminium, aluminium lithium alloy, kamash alloy, lithium silicon close
Gold, lithium titanium alloy class can embedding lithium metal, thickness is 0.5mm~1mm.
Wherein, when afflux porous portion be covered with can intercalation materials of li ions porous conductive layer when, porous conductive layer can be conductive metal layer,
The conductive metal layer is wire netting or woven wire cloth, and mesh is square, rhombus, rectangle or polygon etc.；Or should
Conductive metal layer is the porous foam metal layer with loose structure；Or the conductive metal layer is expanded metal or metal foil
Formed through mechanical stamping or chemical attack, the material of conductive metal layer is stainless steel, nickel, titanium, silver, tin, tin-coated copper or nickel plating
Copper etc..Or porous conductive layer can be electric conduction of carbon fiber cloth, wire and organic fiber silk hybrid conductive cloth, surface coating
Conductive coating or the porous organic material for being coated with metallic film, porous organic material include natural linen-cotton, terylene, aramid fiber, Buddhist nun
Dragon, polypropylene fibre, polyethylene, polytetrafluoroethylene (PTFE) and other electrolyte resistances can be good organic matter.Can intercalation materials of li ions for can embedding lithium
One kind in acieral, silicon-base alloy, kamash alloy, Li-Ti oxide, lithium Si oxide, metallic lithium powder and graphite etc. or
It is a variety of.Can intercalation materials of li ions by being cast, coating, hot-rolling pressure, silk-screen printing, inkjet printing, spraying, bonding, electrochemical plating,
The mode such as chemical plating or machinery press-in invests the surface of porous conductive layer.
In addition, afflux porous portion can be can intercalation materials of li ions, the porous mixture of conductive filler and binding agent or for can embedding lithium material
The porous mixture of material, conductive filler and polyelectrolyte floor.The mass fraction of conductive filler is not less than 70%, can embedding lithium material
Expect that mass fraction is not less than 10%.Wherein, can intercalation materials of li ions for can embedding lithium acieral, silicon-base alloy, kamash alloy, lithium
One or more in titanium oxide, lithium Si oxide, metallic lithium powder and graphite etc.；Conductive filler be carbon black, CNT,
Carbon fiber, graphene, titanium valve, aluminium powder, silver powder, alloy aluminium powder, stainless steel powder or silver powder, rich lithium silica flour, lithium alloys powder
One or more in metalloid alloy conductive particle, or carbon material containing lithium；Binding agent is polyvinyl chloride, polyethylene, gathered
Propylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyimides, polyethers nitrile, polyacrylic acid first
One kind in ester, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose, improved polyalkene etc.
It is or several；Polyelectrolyte floor is the gel polymerisation of polymeric matrix, liquid organic plasticizers and the compound composition of lithium salts three parts
Thing electrolyte composite material.
Advantage of the invention is that：
(1) in lithium slurry battery cathode sheet can embedding lithium afflux structure layer can when charging embedding lithium, particularly when can embedding lithium
Afflux structure layer can prevent the growth of Li dendrite by the theomorphism of slurry when including slurry portion, greatly reduce battery charge and discharge
Lithium is deposited on the possibility that the face of body surface containing lithium metal forms the internal short-circuit of battery caused by Li dendrite when electric；
(2) body containing lithium metal in lithium slurry battery cathode sheet can effectively supplement the formation of negative pole SEI films and electricity as lithium source
Consumption of the side reaction to lithium in the cyclic process of pond, improve the energy density and efficiency of battery；
(3) body containing lithium metal and can embedding lithium afflux structure layer common afflux act on cause negative plate internal current distribution it is more equal
It is even, avoid the fever phenomenon caused by battery high rate charge-discharge.
Brief description of the drawings
Fig. 1 is the schematic diagram of the lithium slurry battery of the present invention；
Fig. 2 is the schematic diagram of the negative plate of the lithium slurry battery of the present invention；
Fig. 3 is the schematic cross-section according to the negative plate of the lithium slurry battery of first embodiment of the invention；
Fig. 4 is the schematic cross-section according to the negative plate of the lithium slurry battery of second embodiment of the invention；
Fig. 5 is the schematic cross-section according to the negative plate of the lithium slurry battery of third embodiment of the invention；
Fig. 6 be negative plate be lithium piece and negative plate be aluminium net and lithium piece composite construction discharge and recharge of the battery under different multiplying
Test chart, wherein, positive pole is the pole piece of LiFePO4 coating, and Fig. 6 (a) negative plate is lithium piece；Fig. 6 (b), (c)
Negative plate for aluminium net and lithium piece composite construction；
Fig. 7 is the test chart of embedding lithium slurry, and Fig. 7 (a) is the charge-discharge test of graphite slurry half-cell；Fig. 7 (b) is positive pole
For the battery charging and discharging test that LiFePO4 pole piece, negative pole are graphite slurry；Fig. 7 (c) is just extremely LiFePO4 pole piece, negative
Extremely tested containing the battery charging and discharging of lithium piece and graphite slurry.
Reference numerals list
1-sandwich anode composite piece
101-porous afflux anode layer
102-electrocondution slurry
2-negative plate
201-insulated enclosure frame
202-can embedding lithium afflux structure layer
203-negative lug
204-afflux porous portion
205-body containing lithium metal
206-slurry portion
207-porous layer
208-sandwich composite construction
3-separate cavities
4-separation layer
Embodiment
Below in conjunction with accompanying drawing, by embodiment, the present invention will be further described.
Fig. 1 is the schematic diagram according to the lithium slurry battery of the present invention.The battery core of lithium slurry battery includes several folders being arranged alternately
Heart anode composite piece 1 and negative plate 2, height is provided between sandwich anode composite piece 1 and negative plate 2 as 0.1mm~1mm's
Separate cavities 3, separate cavities 3 are interior to be full of electrolyte.Sandwich anode composite piece 1 includes porous afflux anode layer 101 and electrocondution slurry
102, porous afflux anode layer 101 is made up of the single or double coating porous anode material layer of porous anode collector, more than two
Oozed between hole afflux anode layer 101 filled with the electrocondution slurry 102 that thickness is 0~5mm, part or all of electrocondution slurry 102
Arrive thoroughly in the hole of porous afflux anode layer 101, form sandwich anode composite piece 1.Negative plate 2 includes can embedding lithium afflux structure
Layer 202 and body containing lithium metal 205, wherein can embedding lithium afflux structure layer 202, body containing lithium metal 205 and it is another can embedding lithium afflux
Structure sheaf 202 forms sandwich composite construction 208.When over-charging of battery or big multiplying power fast charge, lithium ion will not be largely deposited on
The surface of body containing lithium metal 205, but will be embedded into and can avoid and form lithium in negative terminal surface in embedding lithium afflux structure layer 202
Dendrite；Negative pole SEI films are formed pair when other body containing lithium metal 205 can supplement battery charge and discharge process, be particularly initial charge
The consumption of lithium ion；Also, can embedding lithium afflux structure layer 202 and body containing lithium metal 205 can play simultaneously afflux effect, make
Catchment effect is more excellent, evenly, the generation for situations such as avoiding the heating caused by high rate charge-discharge.
Fig. 2 is the schematic perspective view of the negative plate of the lithium slurry battery of the present invention.Negative plate 2 include insulated enclosure frame 201 and
By can embedding lithium afflux structure layer-body containing lithium metal-can the sandwich composite construction 208 that forms of embedding lithium afflux structure layer, insulated enclosure
Frame 201 is arranged on the edge of sandwich composite construction 208, and the insulated enclosure frame 201 is in " returning " font, and with it is sandwich multiple
Close the edge fixing seal of structure.Negative plate 2 also includes negative lug 203, negative lug 203 can with can embedding lithium collection
Flow structure layer 202 electrically connects, or can simultaneously with body containing lithium metal 205 and can embedding lithium afflux structure layer 202 electrically connect.
The outside of sandwich composite construction 208 is also provided with lithium ion can be by and the intransitable separation layer 4 of electronics.
Fig. 3 is the schematic cross-section according to the negative plate of the lithium slurry battery of first embodiment of the invention.In this embodiment,
Can embedding lithium afflux structure layer 202 be afflux porous portion 204, body containing lithium metal 205 is provided between two afflux porous portion 204.
Afflux porous portion 204 can be it is porous can embedding lithium metal conductive layer or be covered with can intercalation materials of li ions porous conductive layer.Herein, collect
Porous portion 204 can either be embedded in lithium ion to stream, and can enough plays a part of collector.Body containing lithium metal 205 is by welding, spraying
The mode of painting, bonding, electrochemical plating, chemical plating or machinery press-in is fixed on afflux porous portion 204.When lithium slurry battery is in mistake
Fill or during big multiplying power fast charge, lithium ion will be embedded into the porous of afflux porous portion 204 can embedding lithium metal or porous, electrically conductive layer surface
Can be in intercalation materials of li ions.So, the Lithium-ion embeding reaction occurred on negative pole will not become deposition of the lithium metal in negative terminal surface,
Therefore avoid and form Li dendrite on the surface of negative plate.
Fig. 4 is the schematic cross-section according to the negative plate of the lithium slurry battery of second embodiment of the invention.In this embodiment,
Can embedding lithium afflux structure layer 202 include afflux porous portion 204 and slurry portion 206.Two can embedding lithium afflux structure layer 202 with starch
The mode that material portion 206 abuts with body containing lithium metal 205 is arranged at the both sides of body containing lithium metal 205.Afflux porous portion 204 can be with
Be it is porous can embedding lithium metal conductive layer or be covered with can intercalation materials of li ions porous conductive layer.Slurry portion 206 for can intercalation materials of li ions, lead
Electric agent and the mixture of electrolyte, wherein, can the volume content of intercalation materials of li ions be 10%~80%, the volume content of conductive agent is
0.1%~5%.In this embodiment, afflux porous portion 204 and slurry portion 206 can be embedded in during charging lithium from
Son.It should be understood that according to the present invention, as long as one of afflux porous portion 204 and slurry portion 206 can be in chargings
During embedded lithium ion.
When lithium slurry battery is overcharging or big multiplying power fast charge, lithium ion will be embedded into the porous of afflux porous portion 204 can embedding lithium gold
Category or porous, electrically conductive layer surface can be in intercalation materials of li ions.So, the Lithium-ion embeding reaction occurred on negative pole will not become lithium gold
Belong to the deposition in negative terminal surface, in addition, the growth of Li dendrite can also be prevented by the theomorphism of slurry.Therefore, avoid
Li dendrite is formed on the surface of negative plate.
In addition, when slurry portion 206 containing can intercalation materials of li ions when, slurry portion 206 also have in charging process store lithium function.
Therefore, in battery discharge procedure, lithium ion, can also be from slurry portion 206 except can be from the deintercalation of body containing lithium metal 205
Deintercalation, add the memory capacity of battery.
Fig. 5 is the schematic cross-section according to the negative plate of the lithium slurry battery of third embodiment of the invention.In this embodiment,
Afflux porous portion 204 is sandwich construction, in addition, the other structures of negative plate 2 and first embodiment shown in Fig. 3 or with figure
Second embodiment shown in 4 is identical.In this embodiment, afflux porous portion 204 includes multiple porous layers 207, Mei Geduo
The material of aperture layer 207, thickness, porosity, pore diameter range can with it is identical, can also be different.For example, afflux porous portion 204
May include two layers of porous layer 207, one layer for it is porous can embedding lithium metal conductive layer, one layer for be covered with can intercalation materials of li ions porous, electrically conductive
Layer or only porous conductive layer.Two layers of porous layer 207 is connected together by the mode such as being bonded, welding.Can be according to reality
Need to adjust material, thickness, porosity and the pore diameter range of each porous layer 207.
Fig. 6 be negative plate be lithium piece and negative plate be aluminium net and lithium piece composite construction discharge and recharge of the battery under different multiplying
Test chart, wherein, positive pole is the pole piece of LiFePO4 coating, and Fig. 6 (a) negative plate is lithium piece；Fig. 6 (b), (c)
Negative plate for aluminium net and lithium piece composite construction.Charging and discharging curve under the different multiplying shown in Fig. 6 (a) and Fig. 6 (b)
Understand, add can after the aluminium net of embedding lithium battery high rate performance it is more excellent, it can be seen that aluminium from Fig. 6 (c) battery charging curve
Net the voltage platform of embedding lithium.
Fig. 7 is the test chart of embedding lithium slurry, and Fig. 7 (a) is the charge-discharge test of graphite slurry half-cell, it can be seen that due to needing
Substantial amounts of lithium is consumed to form SEI films, graphite slurry has nearly 50% ratio of irreversible capacity first, if this part consumes
Lithium all provided by positive pole, the reversible capacity of battery will be substantially reduced；Fig. 7 (b) is just extremely LiFePO4 pole piece, negative
The extremely battery charging and discharging test of graphite slurry, from figure, due to sizable lithium consumption irreversible first, battery is in head
Capacity attenuation is serious after secondary charging；Fig. 7 (c) is that just extremely LiFePO4 pole piece, negative pole are being the battery containing lithium piece and graphite slurry
Charge-discharge test, the lithium piece for mending lithium effect is played due to being provided with negative pole, avoids the capacity attenuation of battery, performance greatly changes
It is kind.
The specific embodiment of the invention is not limited to the present invention.Any those skilled in the art, the present invention is not being departed from
Under technical scheme ambit, many possibility are all made to technical solution of the present invention using the methods and technical content of the disclosure above
Changes and modifications, or be revised as the equivalent embodiment of equivalent variations.Therefore, every content without departing from technical solution of the present invention,
Technical spirit according to the present invention still falls within this hair to any simple modifications, equivalents, and modifications made for any of the above embodiments
In the range of bright technical scheme protection.
Claims (14)
- A kind of 1. negative plate of lithium slurry battery, it is characterised in that：The negative plate include insulated enclosure frame, body containing lithium metal and Can embedding lithium afflux structure layer, it is described can embedding lithium afflux structure layer, the body containing lithium metal and it is another it is described can embedding lithium afflux structure layer Form sandwich composite construction, the insulated enclosure frame seals the edge of the sandwich composite construction, it is described can embedding lithium afflux knot The material of structure layer contain be capable of embedding lithium in lithium slurry battery charge and discharge process can intercalation materials of li ions.
- 2. the negative plate of lithium slurry battery according to claim 1, wherein, it is described can embedding lithium afflux structure layer include afflux Porous portion, the afflux porous portion contain be capable of in lithium slurry battery charge and discharge process embedding lithium can intercalation materials of li ions, the afflux The thickness of porous portion is 0.01 μm~2000 μm, and through hole porosity is 30%~98%, and pore diameter range is 10nm~2mm.
- 3. the negative plate of lithium slurry battery according to claim 1, wherein, it is described can embedding lithium afflux structure layer include afflux Porous portion and slurry portion, the slurry portion and the afflux porous portion be adjacent or the slurry portion in slurry fractions or it is complete Penetrate into portion in the hole of the afflux porous portion,Wherein, described in two can embedding lithium afflux structure layer be arranged on institute in a manner of the slurry portion and the body phase containing lithium metal are adjacent The both sides of the body containing lithium metal are stated,Wherein, the afflux porous portion and/or the slurry portion contain be capable of embedding lithium in lithium slurry battery charge and discharge process can be embedding Lithium material,Wherein, the thickness of the afflux porous portion is 0.01 μm~2000 μm, and through hole porosity is 30%~98%, pore diameter range For 10nm~2mm, the thickness in the slurry portion is 0~2mm.
- 4. the negative plate of lithium slurry battery according to claim 3, wherein, the slurry portion includes electrolyte and can Flow in the electrolytic solution can embedding lithium conductive particle, wherein, it is described can embedding lithium conductive particle account for the mass ratio in the slurry portion and be 10%~90%, average grain diameter is 500nm~500 μm,It is described can embedding lithium conductive particle for can intercalation materials of li ions and conductive agent compound or mixture, wherein, can intercalation materials of li ions with leading The mass ratio of electric agent is 0~98：100~2, compound or mixing mode includes Surface coating, bonding or mechanical mixture, described to lead Electric agent is carbon black, Ketjen black, graphene, CNT, carbon fiber, amorphous carbon or one kind or several in metallic conduction particle Kind.
- 5. the negative plate of the lithium slurry battery according to any one of claim 2-4, wherein, the afflux porous portion includes Single porous layer；Or the afflux porous portion includes multiple porous layers, material, thickness, the hole of each porous layer Rate is identical or different with aperture, and each porous layer is connected to one by way of welding, spray, being bonded or machinery is pressed into Rise.
- 6. the negative plate of the lithium slurry battery according to any one of claim 1-4, wherein, the insulated enclosure frame passes through The mode of hot pressing or stickup is sealingly fixed to the edge of the sandwich composite construction, and the material of the insulated enclosure frame is exhausted The polymeric material of edge electrolyte resistance, it is described insulation electrolyte resistance polymeric material for polyvinyl chloride, polyethylene, polypropylene, It is polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, polyamide, polyimides, polyethers nitrile, PMA, poly- One or more in vinylidene, polyurethane, polyacrylonitrile, butadiene-styrene rubber, sodium carboxymethylcellulose and improved polyalkene.
- 7. the negative plate of the lithium slurry battery according to any one of claim 1-4, wherein, the surface of the negative plate is set There is the separation layer that electronic isolation ion turns on, the material of the separation layer is the nonconducting porous polymer material of electronics；Or The material of the separation layer is the nonconducting inorganic non-metallic material of electronics and the compound porous material of organic polymer；Or institute The material for stating separation layer is the gel of the nonconducting polymeric matrix of electronics, liquid organic plasticizers and the compound composition of lithium salts three parts Polymer electrolytic composite material；Or the material of the separation layer is the hole in the nonconducting porous polymer material of electronics Electrolyte or poly- interior or that ionic conduction is impregnated with the hole of inorganic non-metallic material and the compound porous material of organic polymer Compound colloidal materials.
- 8. the negative plate of lithium slurry battery according to claim 7, wherein, the nonconducting porous polymer material of electronics Expect for polyethylene, polypropylene or Kynoar；The nonconducting inorganic non-metallic material of electronics and organic polymer are compound Porous material is glass fibre non-woven, non-woven fabrics of synthetic fiber or ceramic fiber paper.
- 9. the negative plate of lithium slurry battery according to claim 2, wherein, the material of the body containing lithium metal is lithium metal Or rich lithium alloy, the body containing lithium metal is welding, spray, be bonded, electrochemical plating, chemical plating or machinery press-in by way of Be fixed on it is described can embedding lithium afflux structure layer afflux porous portion.
- 10. the negative plate of the lithium slurry battery according to claim 3 or 4, wherein, the body containing lithium metal, the collection Stream porous portion and the slurry portion are fixedly connected by the insulated enclosure frame.
- 11. the negative plate of the lithium slurry battery according to any one of claim 2-4, wherein, the negative plate is provided with negative Pole lug, the negative lug with it is described can embedding lithium afflux structure layer afflux porous portion electrically connect or with the body containing lithium metal electricity Connection；Or the negative lug with it is described can embedding lithium afflux structure layer afflux porous portion electrically connect and with it is described containing lithium gold Belong to body electrical connection.
- 12. the negative plate of lithium slurry battery according to claim 5, wherein, it is at least one in the afflux porous portion The porous layer for it is porous can embedding lithium metal conductive layer, it is described it is porous can embedding lithium metal conductive layer be wire netting or woven wire cloth, Mesh is square, rhombus, rectangle or polygon；Or it is described it is porous can embedding lithium metal conductive layer be with loose structure Porous foam metal layer；Or it is described it is porous can embedding lithium metal conductive layer be that metallic plate or metal foil are rotten through mechanical stamping or chemistry Erosion forms,It is described it is porous can embedding lithium metal conductive layer material for aluminium, aluminium lithium alloy, kamash alloy, Li-Si alloy, lithium titanium alloy class Can embedding lithium metal, thickness is 0.5mm~1mm.
- 13. the negative plate of lithium slurry battery according to claim 5, wherein, it is at least one in the afflux porous portion The porous layer be covered with can intercalation materials of li ions porous conductive layer,The porous conductive layer is conductive metal layer, and the conductive metal layer is wire netting or woven wire cloth, mesh for it is square, Rhombus, rectangle or polygon；Or the conductive metal layer is the porous foam metal layer with loose structure；Or The conductive metal layer is that metallic plate or metal foil form through mechanical stamping or chemical attack, and the material of the conductive metal layer is not Become rusty steel, nickel, titanium, silver, tin, tin-coated copper or nickel-clad copper；OrThe porous conductive layer is electric conduction of carbon fiber cloth, wire and organic fiber silk hybrid conductive cloth；OrThe porous conductive layer is that surface coats conductive coating or is coated with the porous organic material of metallic film, porous organic material Material includes natural linen-cotton, terylene, aramid fiber, nylon, polypropylene fibre, polyethylene and polytetrafluoroethylene (PTFE),It is described can intercalation materials of li ions for can the acieral of embedding lithium, silicon-base alloy, kamash alloy, Li-Ti oxide, lithium Si oxide, One or more in metallic lithium powder and graphite.
- 14. the negative plate of lithium slurry battery according to claim 5, wherein, it is at least one in the afflux porous portion The porous layer for can intercalation materials of li ions, conductive filler and binding agent porous mixture or for can intercalation materials of li ions, conductive filler with The porous mixture of polyelectrolyte floor, the mass fraction of the conductive filler are not less than 70%, it is described can intercalation materials of li ions matter Measure fraction and be not less than 10%, wherein,It is described can intercalation materials of li ions for can the acieral of embedding lithium, silicon-base alloy, kamash alloy, Li-Ti oxide, lithium Si oxide, One or more in metallic lithium powder and graphite；The conductive filler is carbon black, CNT, carbon fiber, graphene, titanium valve, aluminium powder, silver powder, alloy aluminium powder, no One or more in rust comminuted steel shot or silver powder, rich lithium silica flour, lithium alloys powder metalloid alloy conductive particle and carbon material containing lithium；The binding agent be polyvinyl chloride, polyethylene, polypropylene, polystyrene, polytetrafluoroethylene (PTFE), polyester terephthalate, Polyamide, polyimides, polyethers nitrile, PMA, Kynoar, polyurethane, polyacrylonitrile, butadiene-styrene rubber, One or more in sodium carboxymethylcellulose and improved polyalkene；The polyelectrolyte floor is the gel polymerisation of polymeric matrix, liquid organic plasticizers and the compound composition of lithium salts three parts Thing electrolyte composite material.
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| CN201610621508.2A CN107681115B (en) | 2016-08-01 | 2016-08-01 | Negative plate of lithium slurry battery |
| US16/082,838 US10868337B2 (en) | 2016-03-08 | 2017-03-08 | Cell-core for lithium slurry battery, and lithium slurry battery module |
| PCT/CN2017/075925 WO2017152836A1 (en) | 2016-03-08 | 2017-03-08 | Cell for lithium paste battery, and lithium paste battery module |
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