CN117977044B - Method for recycling sulfide-based all-solid-state battery material - Google Patents
Method for recycling sulfide-based all-solid-state battery material Download PDFInfo
- Publication number
- CN117977044B CN117977044B CN202410383625.4A CN202410383625A CN117977044B CN 117977044 B CN117977044 B CN 117977044B CN 202410383625 A CN202410383625 A CN 202410383625A CN 117977044 B CN117977044 B CN 117977044B
- Authority
- CN
- China
- Prior art keywords
- solvent
- sulfide
- solid
- solid phase
- state battery
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 16
- 238000004064 recycling Methods 0.000 title claims abstract description 14
- 239000003792 electrolyte Substances 0.000 claims abstract description 98
- 239000007790 solid phase Substances 0.000 claims abstract description 93
- 239000011149 active material Substances 0.000 claims abstract description 51
- 238000002156 mixing Methods 0.000 claims abstract description 37
- 238000010438 heat treatment Methods 0.000 claims abstract description 35
- 239000011230 binding agent Substances 0.000 claims abstract description 29
- 239000007787 solid Substances 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 20
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims abstract description 16
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000006258 conductive agent Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims description 157
- 239000007791 liquid phase Substances 0.000 claims description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 14
- 239000000126 substance Substances 0.000 claims description 12
- 239000007774 positive electrode material Substances 0.000 claims description 11
- RXGUIWHIADMCFC-UHFFFAOYSA-N 2-Methylpropyl 2-methylpropionate Chemical compound CC(C)COC(=O)C(C)C RXGUIWHIADMCFC-UHFFFAOYSA-N 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- MLFHJEHSLIIPHL-UHFFFAOYSA-N isoamyl acetate Chemical compound CC(C)CCOC(C)=O MLFHJEHSLIIPHL-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 claims description 8
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 6
- XUPYJHCZDLZNFP-UHFFFAOYSA-N butyl butanoate Chemical compound CCCCOC(=O)CCC XUPYJHCZDLZNFP-UHFFFAOYSA-N 0.000 claims description 6
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 229940117955 isoamyl acetate Drugs 0.000 claims description 5
- 229910009297 Li2S-P2S5 Inorganic materials 0.000 claims description 4
- 229910009311 Li2S-SiS2 Inorganic materials 0.000 claims description 4
- 229910009176 Li2S—P2 Inorganic materials 0.000 claims description 4
- 229910009228 Li2S—P2S5 Inorganic materials 0.000 claims description 4
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 claims description 4
- 229910010848 Li6PS5Cl Inorganic materials 0.000 claims description 4
- 229910010835 LiI-Li2S-P2S5 Inorganic materials 0.000 claims description 4
- 229910010833 LiI-Li2S-SiS2 Inorganic materials 0.000 claims description 4
- 229910010840 LiI—Li2S—P2S5 Inorganic materials 0.000 claims description 4
- 229910010855 LiI—Li2S—SiS2 Inorganic materials 0.000 claims description 4
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 4
- 229940007550 benzyl acetate Drugs 0.000 claims description 4
- 239000002134 carbon nanofiber Substances 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- 229910000921 lithium phosphorous sulfides (LPS) Inorganic materials 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- AOPDRZXCEAKHHW-UHFFFAOYSA-N 1-pentoxypentane Chemical compound CCCCCOCCCCC AOPDRZXCEAKHHW-UHFFFAOYSA-N 0.000 claims description 3
- 229920000459 Nitrile rubber Polymers 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000006229 carbon black Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- GJRQTCIYDGXPES-UHFFFAOYSA-N iso-butyl acetate Natural products CC(C)COC(C)=O GJRQTCIYDGXPES-UHFFFAOYSA-N 0.000 claims description 3
- FGKJLKRYENPLQH-UHFFFAOYSA-M isocaproate Chemical compound CC(C)CCC([O-])=O FGKJLKRYENPLQH-UHFFFAOYSA-M 0.000 claims description 3
- OQAGVSWESNCJJT-UHFFFAOYSA-N isovaleric acid methyl ester Natural products COC(=O)CC(C)C OQAGVSWESNCJJT-UHFFFAOYSA-N 0.000 claims description 3
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 3
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229920002379 silicone rubber Polymers 0.000 claims description 3
- 239000004945 silicone rubber Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims 2
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 23
- 238000012360 testing method Methods 0.000 abstract description 6
- 239000004744 fabric Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 238000001914 filtration Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- OTYYBJNSLLBAGE-UHFFFAOYSA-N CN1C(CCC1)=O.[N] Chemical compound CN1C(CCC1)=O.[N] OTYYBJNSLLBAGE-UHFFFAOYSA-N 0.000 description 2
- 229910018130 Li 2 S-P 2 S 5 Inorganic materials 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 125000002015 acyclic group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 n-sunflower Chemical compound 0.000 description 2
- 150000002825 nitriles Chemical class 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000000101 thioether group Chemical group 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
- H01M10/54—Reclaiming serviceable parts of waste accumulators
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- 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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
- H01M4/623—Binders being polymers fluorinated polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/84—Recycling of batteries or fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for recycling sulfide-based all-solid-state battery materials, and belongs to the technical field of solid-state batteries. The method comprises the following steps: separating out the binder and sulfide electrolyte in the sulfide-based all-solid battery pole piece to obtain a residual solid phase, wherein the residual solid phase contains an active material and a conductive agent; mixing the residual solid phase with lithium sulfate and performing first heat treatment to obtain a modified solid phase; and mixing the modified solid phase with a composite solution containing sulfide electrolyte, and performing a second heat treatment to obtain the active material coated with sulfide electrolyte. The method can effectively recycle the main components of the waste pole piece which is not subjected to the charge-discharge test, and obtain the electrolyte coated active material.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a method for recycling sulfide-based all-solid-state battery materials.
Background
All-solid-state batteries are widely developed because of their high safety and high energy density, and are currently largely classified into sulfide-based, polymer-based, and oxide-based all-solid-state batteries. The sulfide-based solid electrolyte can relieve a solid-solid interface due to soft texture, and the ionic conductivity is high, so that quick charge and quick discharge are mainly developed by various institutions and companies.
The sulfide-based solid-state battery consists of a positive electrode plate, an electrolyte membrane and a negative electrode plate, wherein the electrode plate mainly consists of an active material, sulfide electrolyte, a binder and a conductive agent, wherein the active material accounts for more than 50wt% in order to ensure the energy density of the all-solid-state battery, and the sulfide electrolyte accounts for more than 30wt% in order to ensure the rapid transportation of ions, so that the cost of the active material and the sulfide electrolyte occupies the main cost of the all-solid-state battery. In addition, because the related research at the present stage is mainly in the technology accumulation period, a large number of waste pole pieces which are not subjected to charge and discharge tests exist in an experiment level or a production line, such as unsuitable solid content, off-design of surface density or burr cutting, and the like, a large amount of resource waste is caused, and the waste pole pieces also need professional dangerous waste treatment due to sulfide electrolyte, and expensive cost is generated. Therefore, the recovery of the active materials and/or sulfide electrolyte from such waste sheets is of great economic significance.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a method for recycling sulfide-based all-solid-state battery materials, which can at least recycle active materials in the waste pole pieces.
The application can be realized as follows:
In a first aspect, the present invention provides a method for recovering sulfide-based all-solid-state battery material, comprising the steps of: separating out the binder and sulfide electrolyte in the sulfide-based all-solid battery pole piece to obtain a residual solid phase, wherein the residual solid phase contains an active material and a conductive agent;
mixing the rest solid phase with lithium sulfate and performing first heat treatment to obtain a modified solid phase; and mixing the modified solid phase with a composite solution containing sulfide electrolyte, and performing a second heat treatment to obtain the sulfide electrolyte coated active material.
In an alternative embodiment, the sulfide-based all-solid-state battery pole piece comprises at least one of a positive pole piece and a negative pole piece, and the positive active material in the positive pole piece comprises at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate and lithium iron phosphate; the negative electrode active material in the negative electrode plate comprises at least one of graphite, pure silicon, silicon carbon and lithium titanate;
And/or the sulfide electrolyte includes at least one of Li6PS5Cl、Li3PS4、Li2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Si2S-P2S5、Li2S-P2S5-LiI-LiBr and LiI-Li 2S-P2S5;
And/or the binder comprises at least one of PVDF5130, PVDF900, PVDF-HFP, styrene-butadiene rubber, nitrile rubber, and silicone rubber;
and/or the conductive agent includes at least one of VGCF, CNTs, KS, super P, reduced graphene oxide, and carbon black.
In an alternative embodiment, a method of separating binder from a sulfide-based all-solid state battery pole piece includes: mixing a sulfide-based all-solid-state battery pole piece with a first solvent, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase; the first solvent is a solvent capable of separating the binder from the sulfide electrolyte;
the polarity parameter of the first solvent is less than 5.0.
In an alternative embodiment, the method of separating the binder in the sulfide-based all-solid state battery pole piece has at least one of the following features:
Characteristic one: the mixing of the sulfide-based all-solid-state battery pole piece and the first solvent is that the sulfide-based all-solid-state battery pole piece is soaked in the first solvent;
and the second characteristic is: mixing the sulfide-based all-solid-state battery pole piece with the first solvent for 6-12h at 40-50 ℃;
and (3) the following characteristics: the first solvent includes at least one of a saturated alkane solvent and an acyclic ester solvent;
And four characteristics: before the sulfide-based all-solid-state battery pole piece is mixed with the first solvent, the method further comprises: carrying out water removal treatment on the first solvent;
And fifth feature: after the sulfide-based all-solid-state battery pole piece is mixed with the first solvent, the method further comprises: and removing the first solvent in the first liquid phase to obtain the binder.
In an alternative embodiment, a method of separating sulfide electrolyte in a sulfide-based all-solid state battery pole piece includes: mixing the first solid phase with a second solvent, and then carrying out solid-liquid separation to obtain a second liquid phase and a residual solid phase; the second solvent is a solvent that dissolves the sulfide electrolyte.
In an alternative embodiment, the method of separating sulfide electrolyte in a sulfide-based all-solid state battery pole piece has at least one of the following features:
Characteristic one: the first solid phase substance is mixed with the second solvent by soaking the first solid phase substance in the second solvent;
And the second characteristic is: the first solid phase and the second solvent are mixed for 2-6 hours at the temperature of 20-30 ℃;
And (3) the following characteristics: 500-1000g of the first solid phase substance is correspondingly used for each liter of the second solvent;
and four characteristics: the second solvent includes at least one of an alcohol solvent and a nitrile solvent.
In an alternative embodiment, the first solvent comprises at least one of n-heptane, n-hexane, n-sunflower, butyl butyrate, isobutyl isobutyrate, isobutyl acetate, isoamyl acetate, and n-butyl acetate;
And/or the second solvent comprises at least one of absolute ethanol, methanol, 1-propanol, benzyl alcohol, azamethylpyrrolidone, acetonitrile, and butyronitrile.
In an alternative embodiment, the process of making the sulfide electrolyte coated active material includes at least one of the following features:
characteristic one: the dosage of the lithium sulfate is 1-5wt% of the rest solid phase;
and the second characteristic is: the temperature of the first heat treatment is 500-800 ℃ and the time is 6-12h;
And (3) the following characteristics: the temperature of the second heat treatment is 500-700 ℃ and the time is 3-6h;
And four characteristics: the composite solution comprises an externally added sulfide electrolyte, a third solvent and a fourth solvent; the third solvent comprises at least one of n-sunflower alkane, n-amyl ether, acetophenone and benzyl acetate; the fourth solvent comprises at least one of absolute ethyl alcohol, methanol, 1-propanol, benzyl alcohol, azamethylpyrrolidone, acetonitrile and butyronitrile; or the composite solution includes a third solvent, a portion or all of the second liquid phase.
In an alternative embodiment, mixing the modified solid phase with a sulfide electrolyte-containing composite solution and performing a second heat treatment includes:
Mixing the modified solid phase with an externally added sulfide electrolyte and a fourth solvent, then mixing with a third solvent, performing a second heat treatment, and removing the third solvent and the fourth solvent to obtain an active material coated with the sulfide electrolyte;
Or mixing the modified solid phase with part or all of the second liquid phase, then mixing with a third solvent, and performing a second heat treatment to remove the third solvent and the second solvent in the second liquid phase, thereby obtaining the active material coated with sulfide electrolyte.
In an alternative embodiment, the amount of the third solvent in the composite solution is 1 to 5 times that of the fourth solvent; or the dosage of the third solvent in the composite solution is 1-5 times of that of the second solvent in the second liquid phase.
The beneficial effects of the application include:
The recovery method of sulfide-based all-solid-state battery materials provided by the application can effectively recycle the main components (such as active ingredients) of the waste electrode slices which are not subjected to charge and discharge tests, has great economic benefit, and is beneficial to guaranteeing the performance of active materials.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an SEM image of the original positive electrode active material contained in the positive electrode sheet of the waste sulfide-based all-solid state battery of example 1;
FIG. 2 is an SEM image of the sulfide electrolyte coated active material obtained after the recovery treatment in example 1;
Fig. 3 is an EDS diagram of the sulfide electrolyte coated active material obtained after the recovery treatment in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
The method for recovering sulfide-based all-solid-state battery materials provided by the application is specifically described below.
The application provides a method for recycling sulfide-based all-solid-state battery materials, which comprises the following steps: separating out the binder and sulfide electrolyte in the sulfide-based all-solid battery pole piece to obtain a residual solid phase, wherein the residual solid phase contains an active material and a conductive agent;
mixing the rest solid phase with lithium sulfate and performing first heat treatment to obtain a modified solid phase; and mixing the modified solid phase with a composite solution containing sulfide electrolyte, and performing a second heat treatment to obtain the sulfide electrolyte coated active material.
For reference, the sulfide-based all-solid battery electrode sheet includes at least one of a positive electrode sheet and a negative electrode sheet, the positive electrode active material in the positive electrode sheet may include at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate, and lithium iron phosphate by way of example and not limitation, and the negative electrode active material in the negative electrode sheet may include at least one of graphite, pure silicon, silicon carbon, and lithium titanate by way of example and not limitation.
Sulfide electrolytes can include, by way of example and not limitation, at least one of Li6PS5Cl、Li3PS4、Li2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Si2S-P2S5、Li2S-P2S5-LiI-LiBr and LiI-Li 2S-P2S5, and can also be other sulfide electrolytes useful in the battery arts.
The binder may include, by way of example and not limitation, at least one of PVDF5130, PVDF900, PVDF-HFP, styrene butadiene rubber, nitrile butadiene rubber, and silicone rubber, as well as other binders useful in the battery art.
The conductive agent may include, by way of example and not limitation, at least one of VGCF, CNTs, KS, super P, reduced graphene oxide, and carbon black, and may also be other conductive agents available in the battery art.
For reference, a method of separating out the binder in the sulfide-based all-solid state battery pole piece may include: mixing a sulfide-based all-solid-state battery pole piece with a first solvent, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase; the first solvent is a solvent capable of separating the binder from the sulfide electrolyte.
In some embodiments, prior to mixing the sulfide-based all-solid state battery pole piece with the first solvent, further comprising: the first solvent is subjected to a water removal treatment to prevent water in the solvent from reacting with the sulfide electrolyte, resulting in deterioration of the sulfide electrolyte performance. Preferably, the water content in the first solvent after the water removal treatment is not higher than 50ppm, preferably not higher than 10ppm.
Illustratively, mixing the sulfide-based all-solid state battery pole piece with the first solvent is immersing the sulfide-based all-solid state battery pole piece in the first solvent. The amount of the first solvent is not limited as long as the first solvent can completely dissolve the binder in the sulfide-based all-solid-state battery pole piece.
The mixing of the sulfide-based all-solid-state battery pole piece with the first solvent may be performed at 40-50 c (e.g., 40 c, 42 c, 45 c, 48 c, 50c, etc.) for 6-12h (e.g., 6h, 7h, 8h, 9h, 10h, 11h, 12h, etc.).
In the present application, the first solvent is any solvent capable of achieving separation of the binder from the sulfide electrolyte, including a solvent that dissolves the binder but hardly reacts with the sulfide electrolyte or does not react with the sulfide electrolyte at all. The above "hardly reacts" means that the degree or the speed of the chemical reaction is low, and may be hardly reacted, but not absolutely not reacted. In some embodiments, the first solvent has a polarity parameter of less than 5.0 and may include at least one of a saturated alkane solvent and an acyclic ester solvent, such as, by way of example and not limitation, at least one of n-heptane, n-hexane, n-sunflower, butyl butyrate, isobutyl isobutyrate, isobutyl acetate, isoamyl acetate, and n-butyl acetate.
After the sulfide-based all-solid-state battery pole piece is mixed with the first solvent, solid-liquid separation (namely, filtration solid-liquid separation) can be carried out by using a sieve cloth with 1000-3000 meshes, and then the first solvent in the first liquid phase is removed to obtain the binder. Illustratively, the first liquid phase obtained by the solid-liquid separation may be treated under conditions of 100-150 ℃ (e.g., 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, etc.) to obtain the binder. The treatment time can be 12-24h, such as 12h, 16h, 20h or 24 h.
It should be noted that, at present, the conventional recovery treatment of the waste electrode sheet is generally that the first step is a crushing operation, and large energy is required in the crushing process, and the generated energy directly affects the crystallinity of the active material or sulfide electrolyte, thereby affecting the performance. The application effectively avoids the problems of the crushing treatment by adopting a solvent separation mode, and removes the binder before dissolving the sulfide electrolyte, thereby effectively avoiding the introduction of impurities in the subsequent steps caused by the solvent dissolution of part of the binder for dissolving the sulfide electrolyte in the subsequent steps.
The inventors have proposed that the following problems exist if, in the recovery process of a sulfide-based all-solid-state battery, the sulfide electrolyte is dissolved by using ethanol and then recovered: firstly, the sulfide electrolyte recovered by the mode needs to be applied after high-temperature calcination, the particle diameter of the sulfide electrolyte after calcination is larger, and the contact area with the active material is very limited during the subsequent use; second, since a strong polar organic solvent is used, it is highly likely that part of the binder is dissolved during the treatment, resulting in the sulfide electrolyte after calcination containing impurities.
In the present application, the method for separating sulfide electrolyte in a sulfide-based all-solid battery pole piece may include: mixing the first solid phase with a second solvent, and then carrying out solid-liquid separation to obtain a second liquid phase and a residual solid phase; the second solvent is a solvent that dissolves the sulfide electrolyte.
Similarly, the first solid phase may be mixed with the second solvent by immersing the first solid phase in the second solvent. The mixing of the first solid phase with the second solvent may be carried out at 20-30deg.C (such as 20deg.C, 22deg.C, 24deg.C, 26deg.C, 28deg.C or 30deg.C) for 2-6h (such as 2h, 3h, 4h, 5h or 6 h). 500-1000g (e.g., 500g, 600g, 700g, 800g, 900g, 1000g, etc.) of the first solid phase may be used per liter of the second solvent.
The second solvent may include at least one of an alcohol solvent and a nitrile solvent, such as, by way of example and not limitation, at least one of absolute ethanol, methanol, 1-propanol, benzyl alcohol, azamethylpyrrolidone, acetonitrile, and butyronitrile.
After the first solid phase is mixed with the second solvent, solid-liquid separation (i.e. filtration solid-liquid separation) can be performed by using a sieve cloth with 2000-3000 meshes. The solute in the separated second liquid phase is sulfide electrolyte, and the second solid phase is mainly active material and conductive agent.
In the process of preparing the sulfide electrolyte coated active material, the amount of lithium sulfate is 1-5wt%, such as 1wt%, 1.5wt%, 2wt%, 2.5wt%, 3wt%, 3.5wt%, 4wt%, 4.5wt%, 5wt%, etc. of the rest solid phase.
The temperature of the first heat treatment may be 500-800 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, or the like. The time of the first heat treatment may be 6 to 12 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, or the like.
Specifically, the remaining solid phase may be mixed with lithium sulfate, and then subjected to a first heat treatment in a muffle furnace in a glove box at a heating rate of 10 ℃/min, to obtain a modified solid phase.
In the above steps, a small amount of lithium sulfate is added, so that the carbon originally used as a conductive agent can reduce lithium sulfate at high temperature, and the generated product (lithium sulfide, sulfur, lithium carbonate and the like) can modify the active material, so that side reactions, such as a space charge layer and the like, are avoided when the surface of the active material is coated with sulfide electrolyte, the ion path between the active material and the electrolyte is more smooth, and the performance of the active material is better.
In some embodiments of the present application, the composite solution includes an additional sulfide electrolyte, a third solvent, and a fourth solvent. In other embodiments, the composite solution includes a third solvent, a portion or all of the second liquid phase.
The additional sulfide electrolyte may include, by way of example and not limitation, at least one of Li6PS5Cl、Li3PS4、Li2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Si2S-P2S5、Li2S-P2S5-LiI-LiBr and LiI-Li 2S-P2S5. The third solvent is a solvent which hardly reacts with the sulfide electrolyte or does not react at all with the sulfide electrolyte, and as a reference, the boiling point of the third solvent is not lower than 150 ℃, which may include at least one of n-sunflower, n-amyl ether, acetophenone and benzyl acetate by way of example but not limitation; the fourth solvent may include, by way of example and not limitation, at least one of absolute ethanol, methanol, 1-propanol, benzyl alcohol, azamethylpyrrolidone, acetonitrile, and butyronitrile.
In the present application, the temperature of the second heat treatment may be 500 to 700 ℃, such as 500 ℃, 550 ℃, 600 ℃, 650 ℃, 700 ℃, or the like. The time of the second heat treatment may be 3-6 hours, such as 3 hours, 3.5 hours, 4 hours, 4.5 hours, 5 hours, 5.5 hours, or 6 hours, etc.
In some embodiments, mixing the modified solid phase with a sulfide electrolyte-containing composite solution and performing a second heat treatment includes: mixing the modified solid phase with an externally added sulfide electrolyte and a fourth solvent, then mixing with a third solvent, performing a second heat treatment, and removing the third solvent and the fourth solvent to obtain the sulfide electrolyte coated active material. In the above-mentioned composite solution, the amount of the third solvent may be 1 to 5 times, such as 1,2, 3,4, 5, etc., times that of the fourth solvent. The fourth solvent is used in an amount sufficient to ensure adequate dissolution of the added sulfide electrolyte and adequate dispersion of the modified solid phase therein.
In other embodiments, mixing the modified solid phase with the sulfide electrolyte-containing composite solution and performing a second heat treatment includes: mixing the modified solid phase with part or all of the second liquid phase, then mixing with a third solvent, and performing a second heat treatment to remove the third solvent and the second solvent in the second liquid phase, thereby obtaining the active material coated with sulfide electrolyte. In the above-mentioned composite solution, the amount of the third solvent may be 1 to 5 times, such as 1, 2, 3, 4, 5, etc., times that of the second solvent in the second liquid phase. The amount of the second solvent to be used is only required to ensure sufficient dissolution of the sulfide electrolyte and sufficient dispersion of the modified solid phase therein.
In some specific embodiments, the modified solid phase may be ultrasonically dispersed in part or all of the second liquid phase, the third solvent may be slowly added thereto, then the majority of the solvent may be removed first (e.g., may be performed at 60 ℃), and then transferred to a muffle furnace in a glove box, and subjected to a second heat treatment at a heating rate of 10 ℃/min in an inert atmosphere, thereby obtaining the sulfide electrolyte-coated active material.
In the above steps, after the modified solid phase is dispersed in the second liquid phase, the third solvent is slowly added to form a bi-solvent to control the precipitation process, that is, the sulfide electrolyte originally dissolved in the second liquid phase is slowly precipitated and uniformly nucleates on the surface of the active material in the modified solid phase, so that the sulfide electrolyte is uniformly coated on the surface of the active material. In addition, the modified solid phase is dispersed in the second liquid phase, and the second heat treatment is performed after the third solvent is added, so that the crystallinity of the sulfide electrolyte is improved, and meanwhile, the sulfide electrolyte is ensured to be in large-area contact with the active material, the performance of the active material is ensured, and multiple effects can be achieved without increasing energy consumption compared with the prior art.
As a reference, the particle size of the sulfide electrolyte correspondingly obtained by the recovery method provided by the application is 0.5-5 mu m, and the contact area of the sulfide electrolyte and the active material is wider; in the prior art, the sulfide electrolyte is dissolved by ethanol and then recovered, and the particle size of the obtained sulfide electrolyte is 10-200 mu m, so that the contact area between the sulfide electrolyte and the active material is very limited.
Therefore, the method provided by the application can realize recycling of the main components in the waste pole piece which is not subjected to the charge-discharge test, and simultaneously solve the problem of contact between the recycled sulfide electrolyte and the active material.
On the basis, the recovery method provided by the application is mainly aimed at the waste pole piece which is not subjected to charge and discharge test, and each component in the recovered pole piece can have excellent performance in an initial state to a large extent, and the problems of performance degradation and the like are basically avoided. If the recovery process commonly used in the prior art is adopted for restoration or extraction of metal elements, a large amount of idle work is caused, and the original performance of the components cannot be maintained to a large extent. In addition, the application separates the solid components at different stages by adopting different types of solvents, can realize the effective recovery of each component in the pole piece, and has great economic benefit.
The features and capabilities of the present invention are described in further detail below in connection with the examples.
Example 1
The embodiment provides a method for recycling sulfide-based all-solid-state battery materials, which comprises the following steps:
S1: immersing the positive plate of the waste sulfide-based all-solid-state battery in a first solvent (isobutyl isobutyrate solution) subjected to water removal treatment, so that the isobutyl isobutyrate solution completely submerges the positive plate, and immersing for 8 hours at 40 ℃; filtering with 2000 mesh sieve cloth soaking solution to obtain a first solid phase substance and a first liquid phase substance; and (3) treating the first liquid phase at 100 ℃ for 12 hours to obtain the recovered binder.
The positive plate of the waste sulfide-based all-solid-state battery is from a pole piece coated when the solid content is not proper, the positive active material contained in the positive plate is nickel cobalt lithium manganate, sulfide electrolyte is Li 6PS5 Cl, and the conductive agent is CNTs.
S2: the first solid phase is soaked in a second solvent (absolute ethyl alcohol) at the temperature of 25 ℃ for 4 hours, wherein each liter of the second solvent corresponds to 500g of the first solid phase. Stirring the solution, and then carrying out solid-liquid separation by using a 2000-mesh sieve cloth to obtain a second liquid phase and a residual solid phase.
S3: the remaining solid phase was uniformly mixed with lithium sulfate (the amount of lithium sulfate was 2wt% of the second solid phase), and then transferred to a muffle furnace of a glove box, and treated at 600℃for 8 hours at a heating rate of 10℃per minute, to obtain a modified solid phase.
S4: and (3) ultrasonically dispersing the modified solid phase in a second liquid phase, adding a third solvent (n-sunflower alkane) with the volume of 2 times of that of the second solvent (absolute ethyl alcohol) at the speed of 1L/h, drying at 60 ℃ for 12 hours to remove most of the solvent, transferring into a muffle furnace in a glove box, and treating at the temperature rising rate of 10 ℃/min for 4 hours under an inert atmosphere, so as to obtain the active material coated with sulfide electrolyte.
In this embodiment, SEM images of the original positive electrode active material contained in the positive electrode sheet of the waste sulfide-based all-solid-state battery are shown in fig. 1, SEM images of the sulfide electrolyte coated active material obtained after the recovery treatment are shown in fig. 2, and EDS images of the sulfide electrolyte coated active material obtained after the recovery treatment are shown in fig. 3.
As can be seen from fig. 1, the surface of the original positive electrode active material particles is very smooth; as can be seen from fig. 2, the surface of the recovered positive electrode active material particles is coated with some small particles, and as can be seen from fig. 3, the small particles coated on the surface of the positive electrode active material particles are sulfide electrolytes, and the coated area occupies a relatively large area, so that the method provided by the application has a relatively wide contact area between the recovered sulfide electrolytes and the active materials.
Example 2
The embodiment provides a method for recycling sulfide-based all-solid-state battery materials, which comprises the following steps:
S1: immersing the positive plate of the waste sulfide-based all-solid-state battery in a first solvent (n-heptane solution) subjected to water removal treatment, so that the positive plate is completely submerged by the n-heptane solution, and immersing for 12 hours at 45 ℃; then filtering with 1000 mesh sieve cloth soaking solution to obtain a first solid phase substance and a first liquid phase substance; the first liquid phase was treated at 120℃for 24 hours to obtain a recovered binder.
The positive plate of the waste sulfide-based all-solid-state battery is from a pole piece with the surface density deviating from the design, the positive active material contained in the positive plate is lithium cobaltate, the sulfide electrolyte is Li 2S-P2S5, and the conductive agent is VGCF.
S2: the first solid phase is soaked in a second solvent (nitrogen methyl pyrrolidone) at 20 ℃ for 6 hours, wherein 750g of the first solid phase is corresponding to each liter of the second solvent. Stirring the solution, and then carrying out solid-liquid separation by using 2500-mesh sieve cloth to obtain a second liquid phase and a residual solid phase.
S3: the remaining solid phase was uniformly mixed with lithium sulfate (the amount of lithium sulfate was 1wt% of the second solid phase), and then transferred to a muffle furnace of a glove box, and treated at 500℃for 12 hours at a heating rate of 10℃per minute, to obtain a modified solid phase.
S4: the modified solid phase is dispersed in a second liquid phase by ultrasonic, then a third solvent (acetophenone) with the volume of 1 time of the second solvent (nitrogen methyl pyrrolidone) is added into the modified solid phase at the speed of 1L/h, then the modified solid phase is dried at the temperature of 60 ℃ for 12 hours to remove most of the solvent, then the modified solid phase is transferred into a muffle furnace in a glove box, and the modified solid phase is treated at the temperature rising speed of 10 ℃/min for 6 hours under the inert atmosphere at the temperature rising speed of 500 ℃ to obtain the active material coated by sulfide electrolyte.
Example 3
The embodiment provides a method for recycling sulfide-based all-solid-state battery materials, which comprises the following steps:
S1: immersing the positive plate of the waste sulfide-based all-solid-state battery in a first solvent (isoamyl acetate solution) subjected to water removal treatment, so that the isoamyl acetate solution completely submerges the positive plate, and immersing for 6 hours at 50 ℃; filtering with 3000 mesh sieve cloth soaking solution to obtain a first solid phase substance and a first liquid phase substance; the first liquid phase was treated at 150℃for 18 hours to obtain a recovered binder.
The positive plate of the waste sulfide-based all-solid-state battery is a pole piece with burrs during cutting, the positive active material contained in the positive plate is lithium manganate, the sulfide electrolyte is Li 2S-P2S5, and the conductive agent is Super P (SP).
S2: the first solid phase is soaked in a second solvent (acetonitrile) at the temperature of 30 ℃ for 2 hours, wherein 1000g of the first solid phase is corresponding to each liter of the second solvent. Stirring the solution, and then carrying out solid-liquid separation by using a 3000-mesh sieve cloth to obtain a second liquid phase and a residual solid phase.
S3: the remaining solid phase was uniformly mixed with lithium sulfate (the amount of lithium sulfate was 5wt% of the second solid phase), and then transferred to a muffle furnace of a glove box, and treated at 800 ℃ for 6 hours at a heating rate of 10 ℃/min, to obtain a modified solid phase containing an active material.
S4: and (3) ultrasonically dispersing the modified solid phase in a second liquid phase, adding a third solvent (benzyl acetate) with the volume of 5 times of that of the second solvent (acetonitrile) into the second liquid phase at the speed of 1L/h, drying at 60 ℃ for 12h to remove most of the solvent, transferring the solution into a muffle furnace in a glove box, and treating at 700 ℃ for 3h at the heating rate of 10 ℃/min under an inert atmosphere to obtain the active material coated with sulfide electrolyte.
Example 4
This embodiment differs from embodiment 1 in that:
S4: the modified solid phase and the added Li 6PS5 Cl are dispersed in a fourth solvent together by ultrasonic, then a third solvent (n-sunflower alkane) with the volume of 2 times of that of the fourth solvent (absolute ethyl alcohol) is added into the solution at the speed of 1L/h, then the solution is dried at 60 ℃ for 12 hours to remove most of the solvent, then the solution is transferred into a muffle furnace in a glove box, and the solution is treated for 4 hours at the temperature rising speed of 10 ℃/min under the inert atmosphere, so as to obtain the active material coated by sulfide electrolyte.
Example 5
This example provides a method for recovering sulfide-based all-solid state battery material, which differs from example 1 in that: the waste negative electrode plate is used for replacing the waste sulfide-based all-solid-state battery positive electrode plate, the waste negative electrode plate is from the leftover materials of die cutting, and the negative electrode active material is silicon carbon.
In conclusion, the method for recycling sulfide-based all-solid-state battery materials can effectively recycle the main components of the waste electrode slices which are not subjected to charge and discharge tests, and has great economic benefits. The components in the recovered pole piece can have excellent performance in an initial state to a large extent, the problems of performance degradation and the like are basically avoided, and the recovered sulfide electrolyte and the active material have a wider contact area, so that the performance of the active material is guaranteed.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. The method for recycling sulfide-based all-solid-state battery materials is characterized by comprising the following steps of: separating out the binder and sulfide electrolyte in the sulfide-based all-solid battery pole piece to obtain a residual solid phase, wherein the residual solid phase contains an active material and a conductive agent;
mixing the residual solid phase with lithium sulfate and performing first heat treatment to obtain a modified solid phase; mixing the modified solid phase with a composite solution containing sulfide electrolyte, and performing a second heat treatment to obtain an active material coated with sulfide electrolyte;
the method for separating the binder in the sulfide-based all-solid-state battery pole piece comprises the following steps: mixing the sulfide-based all-solid-state battery pole piece with a first solvent, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase; the first solvent is a solvent capable of separating the binder from the sulfide electrolyte;
The polarity parameter of the first solvent is less than 5.0;
The method for separating sulfide electrolyte in the sulfide-based all-solid-state battery pole piece comprises the following steps: mixing the first solid phase with a second solvent, and then carrying out solid-liquid separation to obtain a second liquid phase and a residual solid phase; the second solvent is a solvent for dissolving sulfide electrolyte;
The first solvent comprises at least one of n-heptane, n-hexane, n-sunflower alkane, butyl butyrate, isobutyl isobutyrate, isobutyl acetate, isoamyl acetate and n-butyl acetate;
The second solvent comprises at least one of absolute ethyl alcohol, methanol, 1-propanol, benzyl alcohol, azomethyl pyrrolidone, acetonitrile and butyronitrile;
The conductive agent comprises at least one of VGCF, CNTs, KS, super P, reduced graphene oxide and carbon black;
the temperature of the first heat treatment is 500-800 ℃ and the time is 6-12h;
The temperature of the second heat treatment is 500-700 ℃ and the time is 3-6h.
2. The recycling method according to claim 1, wherein the sulfide-based all-solid-state battery electrode sheet includes at least one of a positive electrode sheet and a negative electrode sheet, and the positive electrode active material in the positive electrode sheet includes at least one of lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt manganate, and lithium iron phosphate; the negative electrode active material in the negative electrode sheet comprises at least one of pure silicon and lithium titanate;
And/or the sulfide electrolyte includes at least one of Li6PS5Cl、Li3PS4、Li2S-P2S5、Li2S-SiS2、LiI-Li2S-SiS2、LiI-Si2S-P2S5、Li2S-P2S5-LiI-LiBr and LiI-Li 2S-P2S5;
And/or the binder comprises at least one of PVDF5130, PVDF900, PVDF-HFP, styrene-butadiene rubber, nitrile rubber, and silicone rubber.
3. The method of recycling according to claim 1, wherein the method of separating out the binder in the sulfide-based all-solid state battery pole piece has at least one of the following characteristics:
Characteristic one: the sulfide-based all-solid-state battery pole piece is mixed with a first solvent by soaking the sulfide-based all-solid-state battery pole piece in the first solvent;
And the second characteristic is: the mixing of the sulfide-based all-solid-state battery pole piece and the first solvent is carried out for 6-12h at the temperature of 40-50 ℃;
And (3) the following characteristics: the sulfide-based all-solid-state battery pole piece, before being mixed with the first solvent, further comprises: carrying out water removal treatment on the first solvent;
And four characteristics: after the sulfide-based all-solid-state battery pole piece is mixed with the first solvent, the method further comprises: and removing the first solvent in the first liquid phase to obtain the adhesive.
4. The method of claim 1, wherein the method of separating sulfide electrolyte from sulfide-based all-solid-state battery pole pieces has at least one of the following characteristics:
Characteristic one: the first solid phase substance is mixed with the second solvent by soaking the first solid phase substance in the second solvent;
And the second characteristic is: the first solid phase and the second solvent are mixed for 2-6 hours at the temperature of 20-30 ℃;
and (3) the following characteristics: 500-1000g of the first solid phase is used per liter of the second solvent.
5. The method of claim 1, wherein the process of making the sulfide electrolyte coated active material includes at least one of the following features:
characteristic one: the dosage of the lithium sulfate is 1-5wt% of the rest solid phase substance;
And the second characteristic is: the composite solution comprises an externally added sulfide electrolyte, a third solvent and a fourth solvent; the third solvent comprises at least one of n-sunflower alkane, n-amyl ether, acetophenone and benzyl acetate; the fourth solvent comprises at least one of absolute ethyl alcohol, methanol, 1-propanol, benzyl alcohol, azomethyl pyrrolidone, acetonitrile and butyronitrile; or the composite solution comprises a third solvent, part or all of the second liquid phase.
6. The recovery method according to claim 5, wherein mixing the modified solid phase with a composite solution containing a sulfide electrolyte and performing a second heat treatment comprises:
mixing the modified solid phase with the externally added sulfide electrolyte and the fourth solvent, then mixing with a third solvent, performing a second heat treatment, and removing the third solvent and the fourth solvent to obtain a sulfide electrolyte coated active material;
Or mixing the modified solid phase with part or all of the second liquid phase, then mixing with a third solvent, and performing a second heat treatment to remove the third solvent and the second solvent in the second liquid phase, thereby obtaining the active material coated with sulfide electrolyte.
7. The recovery method according to claim 6, wherein the amount of the third solvent in the composite solution is 1 to 5 times that of the fourth solvent; or the dosage of the third solvent in the composite solution is 1-5 times of that of the second solvent in the second liquid phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410383625.4A CN117977044B (en) | 2024-04-01 | 2024-04-01 | Method for recycling sulfide-based all-solid-state battery material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410383625.4A CN117977044B (en) | 2024-04-01 | 2024-04-01 | Method for recycling sulfide-based all-solid-state battery material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117977044A CN117977044A (en) | 2024-05-03 |
| CN117977044B true CN117977044B (en) | 2024-07-16 |
Family
ID=90853582
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410383625.4A Active CN117977044B (en) | 2024-04-01 | 2024-04-01 | Method for recycling sulfide-based all-solid-state battery material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117977044B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN118572239A (en) * | 2024-08-02 | 2024-08-30 | 上海屹锂新能源科技有限公司 | Method for recycling wet sulfide electrolyte membrane waste |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015189053A1 (en) * | 2014-06-13 | 2015-12-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing alkali metal sulphide nanoparticles, alkali metal sulphide nanoparticles, use of the alkali metal sulphide nanoparticles, and alkali metal sulphur battery |
| WO2023191598A1 (en) * | 2022-03-31 | 2023-10-05 | 주식회사 엘지에너지솔루션 | Cathode for all-solid-state battery, and all-solid-state battery comprising same |
Family Cites Families (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4404928B2 (en) * | 2007-10-18 | 2010-01-27 | トヨタ自動車株式会社 | Method for producing coated positive electrode active material, method for producing positive electrode for non-aqueous secondary battery, and method for producing non-aqueous secondary battery |
| JP5277859B2 (en) * | 2007-12-03 | 2013-08-28 | セイコーエプソン株式会社 | Sulfide-based lithium ion conductive solid electrolyte glass and all-solid lithium secondary battery |
| GB2464455B (en) * | 2008-10-14 | 2010-09-15 | Iti Scotland Ltd | Lithium-containing transition metal sulfide compounds |
| JP5551880B2 (en) * | 2009-02-20 | 2014-07-16 | 三星電子株式会社 | All solid state secondary battery |
| JP5673323B2 (en) * | 2011-04-19 | 2015-02-18 | トヨタ自動車株式会社 | Electrode for solid electrolyte battery containing sulfur and method for producing the same |
| JP5578280B2 (en) * | 2011-05-26 | 2014-08-27 | トヨタ自動車株式会社 | Coated active material and lithium solid state battery |
| WO2015080502A1 (en) * | 2013-11-29 | 2015-06-04 | 한양대학교 산학협력단 | Active material for all-solid lithium secondary battery, method for manufacturing same, and all-solid lithium secondary battery comprising same |
| CN107078296B (en) * | 2014-10-27 | 2020-09-29 | 国立大学法人横浜国立大学 | Method for producing cathode material for lithium-sulfur battery, and lithium-sulfur battery |
| KR20190066792A (en) * | 2017-12-06 | 2019-06-14 | 현대자동차주식회사 | A method for manufacturing a sulfide-based solid electrolyte having crystal structure of argyrodite |
| CN110661051B (en) * | 2018-06-28 | 2021-01-22 | 宁德时代新能源科技股份有限公司 | Solid-state battery material recovery processing method |
| CN111313018B (en) * | 2019-12-06 | 2022-04-29 | 中国科学院苏州纳米技术与纳米仿生研究所 | Nano carbon/lithium sulfide composite material and preparation method and application thereof |
| WO2021119295A1 (en) * | 2019-12-10 | 2021-06-17 | The Regents Of The University Of California | Recycling all solid-state battery technology |
| US20230044210A1 (en) * | 2019-12-27 | 2023-02-09 | Semiconductor Energy Laboratory Co., Ltd. | Positive Electrode Active Material Layer, Active Material Layer, Positive Electrode, Secondary Battery, and Vehicle |
| KR20210158233A (en) * | 2020-06-23 | 2021-12-30 | 주식회사 엘지에너지솔루션 | Reuse method of active material of positive electrode scrap |
| US20220384867A1 (en) * | 2021-01-06 | 2022-12-01 | Solid Power Operating, Inc. | Method for separation, segregation, and recovery of constituent materials from electrochemical cells |
| CN114204151A (en) * | 2021-12-06 | 2022-03-18 | 中国矿业大学 | Method for repairing and modifying waste lithium ion battery positive electrode active material |
| KR20230145831A (en) * | 2022-04-11 | 2023-10-18 | 삼성에스디아이 주식회사 | Positive electrode for all solid state battery, preparing method thereof, and all solid state battery |
| CN116598443A (en) * | 2023-02-07 | 2023-08-15 | 深圳市德方创域新能源科技有限公司 | Positive electrode lithium supplementing material, preparation method and application thereof |
| CN117410463A (en) * | 2023-10-18 | 2024-01-16 | 中国科学院青岛生物能源与过程研究所 | Composite positive electrode material for sulfide solid-state battery, and preparation method and application thereof |
-
2024
- 2024-04-01 CN CN202410383625.4A patent/CN117977044B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015189053A1 (en) * | 2014-06-13 | 2015-12-17 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Method for producing alkali metal sulphide nanoparticles, alkali metal sulphide nanoparticles, use of the alkali metal sulphide nanoparticles, and alkali metal sulphur battery |
| WO2023191598A1 (en) * | 2022-03-31 | 2023-10-05 | 주식회사 엘지에너지솔루션 | Cathode for all-solid-state battery, and all-solid-state battery comprising same |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117977044A (en) | 2024-05-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN117977044B (en) | Method for recycling sulfide-based all-solid-state battery material | |
| JP7371263B2 (en) | How to reuse active materials using cathode scraps | |
| Yang et al. | Direct recovery of degraded LiCoO2 cathode material from spent lithium-ion batteries: Efficient impurity removal toward practical applications | |
| CN104105803B (en) | The recovery method of lithium | |
| CN111439748B (en) | Regenerated graphite material and preparation method thereof | |
| WO2021102842A1 (en) | Method for producing lithium iron phosphate precursor by using retired lithium iron phosphate battery as raw material | |
| CN111430831B (en) | Method for recovering waste lithium ion battery negative electrode material | |
| CN106992329B (en) | A kind of resource utilization reuse method of waste and old lithium ion battery lithium iron phosphate positive material | |
| CN109768344A (en) | A kind of separation method of the anode pole piece of waste lithium iron phosphate battery | |
| CN106992328A (en) | The waste lithium iron phosphate positive electrode method that recycling is recycled in Hawkins cell | |
| KR20210145454A (en) | Reuse method of active material of positive electrode scrap | |
| CN109825846A (en) | A kind of method of molten caustic soda electrolytic regeneration waste lithium ion cell anode material | |
| CN110364778B (en) | Method for recovering waste lithium ion battery negative plate | |
| CN113381088B (en) | Method for separating positive active material and aluminum current collector in waste lithium ion battery in a transcritical fluid strengthening way | |
| CN115241555A (en) | Method for recycling waste battery negative electrode graphite | |
| CN114447465A (en) | Method and material for synergistically regenerating anode material and cathode material of lithium ion battery and application of material | |
| CN114024055A (en) | Short-process recovery method for waste lithium iron phosphate battery material | |
| CN117477083A (en) | Recycling and regenerating method of graphite anode material of waste lithium ion battery and application of recycling and regenerating method | |
| CN105591104B (en) | A kind of iron phosphate lithium electrode and preparation method thereof for alkaline secondary cell negative electrode | |
| KR20210145456A (en) | Reuse method of active material of positive electrode scrap | |
| CN116282000A (en) | Method for recycling waste battery graphite carbon slag and co-producing regenerated graphite active material | |
| CN116315214A (en) | Pyrolysis and reduction cooperative treatment method for waste lithium battery pole pieces | |
| CN117185319A (en) | Method for recovering lithium iron phosphate battery through sulfate air roasting | |
| CN115799694A (en) | Crushing, disassembling and recycling method for lithium battery | |
| GB2621300A (en) | Method for regenerating lithium battery positive electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |