CN109980183A - Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment - Google Patents
Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment Download PDFInfo
- Publication number
- CN109980183A CN109980183A CN201711443504.0A CN201711443504A CN109980183A CN 109980183 A CN109980183 A CN 109980183A CN 201711443504 A CN201711443504 A CN 201711443504A CN 109980183 A CN109980183 A CN 109980183A
- Authority
- CN
- China
- Prior art keywords
- atomic layer
- layer deposition
- state battery
- positive
- solid state
- 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.)
- Pending
Links
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 57
- 230000007704 transition Effects 0.000 claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 239000006258 conductive agent Substances 0.000 claims abstract description 11
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000002245 particle Substances 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 7
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 239000007787 solid Substances 0.000 claims description 52
- 239000007784 solid electrolyte Substances 0.000 claims description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 238000004513 sizing Methods 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 229920000379 polypropylene carbonate Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910000521 B alloy Inorganic materials 0.000 claims description 5
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000002002 slurry Substances 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 4
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229910001305 LiMPO4 Inorganic materials 0.000 claims description 3
- 229910015694 LiNi0.85Co0.1Al0.05O2 Inorganic materials 0.000 claims description 3
- 229910014422 LiNi1/3Mn1/3Co1/3O2 Inorganic materials 0.000 claims description 3
- 229910012305 LiPON Inorganic materials 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 229910000676 Si alloy Inorganic materials 0.000 claims description 3
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000006230 acetylene black Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- 229920000867 polyelectrolyte Polymers 0.000 claims description 3
- 229920000193 polymethacrylate Polymers 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 238000010129 solution processing Methods 0.000 claims description 2
- 150000003457 sulfones Chemical class 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims 1
- 238000000151 deposition Methods 0.000 abstract description 11
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000011267 electrode slurry Substances 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000005518 polymer electrolyte Substances 0.000 abstract description 3
- 230000001351 cycling effect Effects 0.000 abstract 2
- 238000007599 discharging Methods 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 230000008021 deposition Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical group 0.000 description 3
- 239000005486 organic electrolyte Substances 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 229920005601 base polymer Polymers 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- 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
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0428—Chemical vapour deposition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- 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
Abstract
The invention relates to a method for improving the cycling stability of a positive electrode for a solid-state battery by atomic layer deposition treatment. The invention belongs to the technical field of solid-state batteries. A method for improving the cycling stability of a positive electrode for a solid-state battery through atomic layer deposition treatment adopts the following two process procedures, namely, mixing a positive electrode active material, a conductive agent, a binder and an organic solvent, obtaining positive electrode slurry through ball milling or stirring, coating the positive electrode slurry on a positive electrode current collector, and drying; processing the anode electrode by atomic layer deposition, and depositing a transition layer in gaps and on the surface of particles of the anode electrode; spraying or coating the polymer electrolyte solution on the surface of the electrode, and drying; secondly, mixing the positive active material, a conductive agent, a binder, a polymer, lithium salt and an organic solvent, coating the mixture on a positive current collector, and drying the mixture; and (3) processing the anode electrode by atomic layer deposition, and depositing a transition layer in the gaps and on the surface of the anode electrode particles. The invention has the advantages of greatly improving the stability of the solid-state battery in the charging and discharging process and the like.
Description
Technical field
The invention belongs to solid state cell technology fields, promote solid state battery more particularly to a kind of processing of atomic layer deposition and use
The method of positive cyclical stability.
Background technique
Currently, due to largely using the inflammable organic electrolytes such as esters, ethers, existing serious in lithium ion battery
Security risk, when battery because when any reason short circuit, battery self-energy can release in the form of heat in the short time, point
These ethers as solvent are fired, explosion is caused.With the solid state lithium battery of solid electrolyte substitution organic electrolyte, it is expected to thoroughly
The safety issue of battery is solved, thus solid electrolyte replaces the solid state lithium battery of traditional liquid organic electrolyte just attracting more
Carry out more concerns.
Current solid state battery still continues to use the positive material such as cobalt acid lithium, LiMn2O4 and LiFePO 4 of conventional lithium ion battery
Material, and the energy density of solid state battery depends primarily on positive electrode, thus screen the novel anode material with high-energy density
It is very important for material.But in solid state battery development process, since solid electrolyte material is different from liquid electrolyte, one
The positive electrodes such as aspect high capacity and high voltage may be unstable with electrolyte chemistry or electrochemistry, for another aspect,
Volume deformation of the positive electrode in charge and discharge process causes electrode active material to disengage with solid electrolyte, these two aspects
Positive active material capacity attenuation is all caused, it is poor so as to cause solid state battery cyclical stability.
Summary of the invention
The present invention is to solve high energy positive electrode stability present in solid state battery system present in well-known technique
Difference, the problems such as cycle life is short, and the side that a kind of atomic layer deposition processing promotes solid state battery anode cyclical stability is provided
Method.
One layer of cause of deposition inside solid state battery anode using technique for atomic layer deposition that the object of the present invention is to provide a kind of
Close transition zone can inhibit the volume expansion in positive active material charge and discharge process, isolation positive active material and electrolysis
The physical contact of material, while there is ion ducting capacity, it is greatly steady in promotion solid state battery anode charge and discharge process
The atomic layer deposition processing of the features such as qualitative promotes the solid state battery method of positive cyclical stability.
Atomic layer deposition (ALD) is by the way that vaporous precursors pulse is alternately passed through reactor and is changed on the deposition substrate
A kind of technology for adsorbing and react and formed deposition film is learned, which can be plated substance with monatomic form membrane layer by layer
In substrate surface.For technique for atomic layer deposition due to the highly controllable type (thickness, composition and structure) of its deposition parameter, excellent is heavy
Product uniformity and consistency make it have a wide range of applications potentiality in the fields such as micro-nano electronics and nano material.According to the technology
Reaction principle feature, all kinds of different materials can be deposited, and deposited material includes metal, oxide, carbon
(nitrogen, sulphur, silicon) compound, classes of semiconductors material and superconductor etc..
Atomic layer deposition processing of the present invention promotes the solid state battery method of positive cyclical stability, the specific steps are as follows:
Scheme (one):
1. prepared by electrode: positive electrode active materials, conductive agent, binder and organic solvent being mixed, by ball milling or stirred
It mixes to obtain anode sizing agent, anode sizing agent is coated on plus plate current-collecting body, electrode is obtained after drying.
2. atomic layer deposition handles anode electrode: 1) anode electrode is placed in atomic layer deposition apparatus chamber, it will
Vaporous precursors pulse is passed through chamber reaction, to deposit transition zone in anode electrode particle voids and surface.
3. solid electrolyte solution is handled: polyelectrolyte solution is sprayed or is coated in the 2) electrode surface, it
Drying obtains solid state battery anode electrode afterwards.
4. battery assembly: 3) anode electrode successively being filled with solid electrolyte film, negative electrode layer stacked group, solid-state electricity is obtained
Pond.
Scheme (two):
1. electrode preparation flow: positive electrode active materials, conductive agent, binder, polymer, lithium salts and organic solvent are mixed
It closes, by ball milling or stirs to get anode sizing agent, anode sizing agent is coated on plus plate current-collecting body, positive electricity is obtained after drying
Pole.
2. atomic layer deposition handles anode electrode: 1) anode electrode is placed in atomic layer deposition apparatus chamber, it will
Vaporous precursors pulse is passed through chamber reaction, to deposit transition zone in anode electrode particle voids and surface.
3. battery assembly: 2) anode electrode successively being filled with solid electrolyte film, negative electrode layer stacked group, solid-state electricity is obtained
Pond.
Positive electrode active materials include but is not limited to LiNi0.85Co0.1Al0.05O2、LiNi1/3Mn1/3Co1/3O2、CrxOy、
LiMPO4One of (M=Fe, Mn).
Conductive agent is Super p, acetylene black, gas phase generate carbon fiber (VGCF), carbon nanotube (CNTs), in graphene
It is one or more of.
Binder is Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), polytetrafluoroethylene (PTFE)
One or more of (PTFE).
Polymer is polyethylene glycol oxide (PEO), polyethylene glycol (PEG), polyacrylonitrile (PAN), polymethacrylates
(PMMA), one or more of polypropylene carbonate (PPC).
Lithium salts is lithium hexafluoro phosphate (LiPF6), lithium perchlorate (LiClO4), LiBF4 (LiBF4), double trifluoro methylsulphurs
One or more of imide li (LiTFSI).
Organic solvent is tetrahydrofuran, acetone, acetonitrile, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl Asia
One or more of sulfone.
Atomic layer deposition transition zone includes but is not limited to Al2O3、Li3PO4, one or more of LiPON.Atomic layer deposition
Product transition region thickness is 2~20nm.
Solid electrolyte film be one or more of LATP, LAGP, LLZO, LPS, LGPS or its with PEO base, PAN base,
The composite membrane of PMMA base or PPC base polymer electrolyte.
Cathode is one or more of lithium metal, lithium-aluminium alloy, Li-Si alloy, lithium boron alloy.
The technical side that the method that atomic layer deposition processing of the present invention promotes the positive cyclical stability of solid state battery is taken
Case is:
A kind of method of the positive cyclical stability of atomic layer deposition processing promotion solid state battery, its main feature is that: atomic layer
Deposition processes promote solid state battery and use following two technical process with the method for positive cyclical stability, first is that, electrode preparation:
Positive electrode active materials, conductive agent, binder and organic solvent are mixed, by ball milling or stir to get anode sizing agent, it will just
Pole slurry is coated on plus plate current-collecting body, and anode electrode is obtained after drying；Atomic layer deposition handles anode electrode: anode electrode is set
In atomic layer deposition apparatus chamber, vaporous precursors pulse is passed through chamber reaction, in anode electrode particle voids and table
Face deposits transition zone；Solid electrolyte solution processing: polyelectrolyte solution is sprayed or is coated in electrode surface, is dried
To solid state battery anode electrode；Second is that electrode preparation flow: by positive electrode active materials, conductive agent, binder, polymer, lithium salts
And organic solvent mixing, by ball milling or anode sizing agent is stirred to get, anode sizing agent is coated on plus plate current-collecting body, is dried
After obtain anode electrode；Atomic layer deposition handles anode electrode: anode electrode is placed in atomic layer deposition apparatus chamber, by gas phase
Presoma pulse is passed through chamber reaction, to deposit transition zone in anode electrode particle voids and surface.
The method that atomic layer deposition processing of the present invention promotes the positive cyclical stability of solid state battery can also use as follows
Technical solution:
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: anode
Active material is LiNi0.85Co0.1Al0.05O2、LiNi1/3Mn1/3Co1/3O2、CrxOy、LiMPO4One of M=Fe, Mn.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: it is conductive
Agent is Super p, acetylene black, gas phase generate one or more of carbon fiber, carbon nanotube, graphene.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: bonding
Agent is one or more of Kynoar, Kynoar-hexafluoropropene, polytetrafluoroethylene (PTFE).
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: polymerization
Object is one or more of polyethylene glycol oxide, polyethylene glycol, polyacrylonitrile, polymethacrylates, polypropylene carbonate.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: lithium salts
For one or more of lithium hexafluoro phosphate, lithium perchlorate, LiBF4, bis-trifluoromethylsulfoandimide lithium.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: it is organic
Solvent be one of tetrahydrofuran, acetone, acetonitrile, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl sulfoxide or
It is several.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: atom
Layer deposition transition zone is Al2O3、Li3PO4, one or more of LiPON.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: atom
Layer deposition transition region thickness is 2~20nm.
The atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, its main feature is that: anode
Electrode is successively filled with solid electrolyte film, negative electrode layer stacked group, obtains solid state battery；Solid electrolyte film be LATP, LAGP,
One or more of LLZO, LPS, LGPS or it is compound with PEO base, PAN base, PMMA base or PPC base polymer electrolyte
Film；Cathode is one or more of lithium metal, lithium-aluminium alloy, Li-Si alloy, lithium boron alloy.
The advantages and positive effects of the present invention are:
The method that atomic layer deposition processing promotes the positive cyclical stability of solid state battery is completely new due to using the present invention
Technical solution, compared with prior art, the present invention using technique for atomic layer deposition solid state battery anode inside deposit one layer
Fine and close transition zone, on the one hand the transition zone can inhibit the volume expansion in positive active material charge and discharge process, another party
The face transition zone has completely cut off the physical contact of positive active material and electrolyte, while there is the transition zone ion energy is connected
Power, therefore can greatly promote the stability in solid state battery anode charge and discharge process.
Detailed description of the invention
Fig. 1 is the processing anode of atomic layer described in embodiment 2 front and back solid state battery cyclic curve.It can be seen from the figure that place
Cell positive material capacity attenuation quickly, is greatly improved using cyclical stability after atomic layer deposition transition zone before managing.
Specific embodiment
In order to further understand the content, features and effects of the present invention, the following examples are hereby given, and cooperate attached drawing
Detailed description are as follows:
Refering to attached drawing 1.
Embodiment 1
A kind of method that atomic layer deposition processing promotion solid state battery uses positive cyclical stability, technical process:
1. weighing 1.6g LiNi0.85Co0.1Al0.05O2、0.2g SP、0.05g PVDF、0.05g PEO、0.025g
LiTFSI, is added 10ml THF solvent after mixing, 50 DEG C of stirring 6h obtain electrode slurry.
2. 1) gained slurry is coated on aluminium foil using 0.3mm scraper, 60 DEG C of drying, later 60 DEG C of vacuum drying 6h.
3. 2) the electrode obtained piece is placed in atomic layer deposition apparatus, use trimethyl aluminium for vaporous precursors, it is heavy through 8
The Al that product cyclic deposition thickness is about 3nm2O3Transition zone, later by electrode cutting at 16 disk of φ.
4. 3) gained anode pole piece is attached at thick 0.15mm, on the LAGP electrolyte sheet of 20 size of φ, electrolyte sheet is another
Side attaches 16 lithium boron alloy piece of φ, is packaged test using buckle battery mouth sealer.2.5~4.2V of voltage range, electric current
Density 20mA/g.
Embodiment 2
A kind of method that atomic layer deposition processing promotion solid state battery uses positive cyclical stability, technical process:
1. weighing 1.7g CrxOy, 0.2g SP, 0.1g PVDF, after mixing be added 20ml nmp solvent, stirring 3h obtain electricity
Pole slurry.
2. 1) gained slurry is coated on aluminium foil using 0.15mm scraper, 100 DEG C of drying, 100 DEG C of vacuum drying later
6h。
3. 2) the electrode obtained piece is placed in atomic layer deposition apparatus, use trimethyl aluminium for vaporous precursors, through 30
The Al that deposition cycle deposition thickness is about 10nm2O3Transition zone, later by electrode cutting at 16 disk of φ.
4. by 1g PEO and 0.5g LiPF6Mixing is dissolved in 10ml acetonitrile, by anode pole piece obtained by coating c) of 0.5ml solution
On, 50 DEG C of drying 12h.
5. 4) gained anode pole piece is attached at thick 0.3mm, on the LATP electrolyte sheet of 20 size of φ, electrolyte sheet is another
Side attaches 16 lithium boron alloy piece of φ, is packaged test using buckle battery mouth sealer.1.5~4.0V of voltage range, electric current are close
Spend 50 μm/cm2。
The present embodiment deposits one layer of fine and close transition zone, a side inside solid state battery anode using technique for atomic layer deposition
The face transition zone can inhibit the volume expansion in positive active material charge and discharge process, and on the other hand the transition zone has completely cut off just
The physical contact of pole active material and electrolyte, while the transition zone has ion ducting capacity, therefore can be greatly
Promote the stability in solid state battery anode charge and discharge process.
Claims (10)
1. a kind of atomic layer deposition processing promotes the solid state battery method of positive cyclical stability, it is characterized in that: atomic layer deposition
Product processing promotes solid state battery and uses following two technical process with the method for positive cyclical stability, first is that, electrode preparation: will
Positive electrode active materials, conductive agent, binder and organic solvent mixing, by ball milling or stir to get anode sizing agent, will be positive
Slurry is coated on plus plate current-collecting body, and anode electrode is obtained after drying；Atomic layer deposition handles anode electrode: anode electrode is placed in
In atomic layer deposition apparatus chamber, vaporous precursors pulse is passed through chamber reaction, on anode electrode particle voids and surface
Deposit transition zone；Solid electrolyte solution processing: polyelectrolyte solution being sprayed or is coated in electrode surface, and drying obtains
Solid state battery anode electrode；Second is that electrode preparation flow: by positive electrode active materials, conductive agent, binder, polymer, lithium salts with
And organic solvent mixing, by ball milling or anode sizing agent is stirred to get, anode sizing agent is coated on plus plate current-collecting body, after drying
Obtain anode electrode；Atomic layer deposition handles anode electrode: anode electrode is placed in atomic layer deposition apparatus chamber, before gas phase
It drives body pulse and is passed through chamber reaction, to deposit transition zone in anode electrode particle voids and surface.
2. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
It is characterized in: positive electrode active materials LiNi0.85Co0.1Al0.05O2、LiNi1/3Mn1/3Co1/3O2、CrxOy、LiMPO4In M=Fe, Mn
One kind.
3. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: conductive agent is Super p, acetylene black, gas phase generate one or more of carbon fiber, carbon nanotube, graphene.
4. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: binder is one or more of Kynoar, Kynoar-hexafluoropropene, polytetrafluoroethylene (PTFE).
5. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: polymer is polyethylene glycol oxide, polyethylene glycol, polyacrylonitrile, polymethacrylates, one in polypropylene carbonate
Kind is several.
6. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: lithium salts is one or more of lithium hexafluoro phosphate, lithium perchlorate, LiBF4, bis-trifluoromethylsulfoandimide lithium.
7. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: organic solvent is tetrahydrofuran, acetone, acetonitrile, N-Methyl pyrrolidone, N,N-dimethylformamide, dimethyl Asia
One or more of sulfone.
8. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: atomic layer deposition transition zone is Al2O3、Li3PO4, one or more of LiPON.
9. atomic layer deposition processing according to claim 1 or 8 promotes the solid state battery method of positive cyclical stability,
It is characterized in that: atomic layer deposition transition region thickness is 2~20nm.
10. atomic layer deposition processing according to claim 1 promotes the solid state battery method of positive cyclical stability,
Be characterized in: anode electrode is successively filled with solid electrolyte film, negative electrode layer stacked group, obtains solid state battery；Solid electrolyte film is
One or more of LATP, LAGP, LLZO, LPS, LGPS or itself and PEO base, PAN base, PMMA base or PPC based polyalcohol electricity
Solve the composite membrane of matter；Cathode is one or more of lithium metal, lithium-aluminium alloy, Li-Si alloy, lithium boron alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711443504.0A CN109980183A (en) | 2017-12-27 | 2017-12-27 | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711443504.0A CN109980183A (en) | 2017-12-27 | 2017-12-27 | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109980183A true CN109980183A (en) | 2019-07-05 |
Family
ID=67072062
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711443504.0A Pending CN109980183A (en) | 2017-12-27 | 2017-12-27 | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109980183A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931713A (en) * | 2019-12-13 | 2020-03-27 | 华中科技大学 | Lithium ion battery anode and preparation method thereof |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112885986A (en) * | 2021-01-29 | 2021-06-01 | 湖南美尼科技有限公司 | Positive pole piece for high-rate solid-state battery and preparation method |
| CN116741947A (en) * | 2023-06-01 | 2023-09-12 | 深圳市原速光电科技有限公司 | Preparation method and application of battery pole piece |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN103022415A (en) * | 2011-09-26 | 2013-04-03 | 比亚迪股份有限公司 | Positive pole, preparation method thereof and lithium-ion battery |
| CN103367712A (en) * | 2013-07-26 | 2013-10-23 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium ion battery coating pole piece |
| CN107195859A (en) * | 2017-05-19 | 2017-09-22 | 中国电子科技集团公司第十八研究所 | Preparation method of dispersion battery |
| CN107240684A (en) * | 2017-06-08 | 2017-10-10 | 华中科技大学 | The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified |
| CN107452954A (en) * | 2017-09-21 | 2017-12-08 | 清陶（昆山）能源发展有限公司 | A kind of lithium-rich manganese-based composite positive pole of solid state battery and preparation method thereof |
-
2017
- 2017-12-27 CN CN201711443504.0A patent/CN109980183A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102244231A (en) * | 2010-05-14 | 2011-11-16 | 中国科学院物理研究所 | Method for cladding surfaces of active material of anode and/or anode and methods manufacturing anode and battery |
| CN103022415A (en) * | 2011-09-26 | 2013-04-03 | 比亚迪股份有限公司 | Positive pole, preparation method thereof and lithium-ion battery |
| CN103367712A (en) * | 2013-07-26 | 2013-10-23 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium ion battery coating pole piece |
| CN107195859A (en) * | 2017-05-19 | 2017-09-22 | 中国电子科技集团公司第十八研究所 | Preparation method of dispersion battery |
| CN107240684A (en) * | 2017-06-08 | 2017-10-10 | 华中科技大学 | The preparation method and product for the nickelic positive electrode of lithium battery that a kind of surface is modified |
| CN107452954A (en) * | 2017-09-21 | 2017-12-08 | 清陶（昆山）能源发展有限公司 | A kind of lithium-rich manganese-based composite positive pole of solid state battery and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YOON SEOK JUNG, ANDREW S. CAVANAGH, LEAH A. RILEY等: "Ultrathin Direct Atomic Layer Deposition on Composite Electrodes for Highly Durable and Safe Li-Ion Batteries", 《ADV. MATER.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110931713A (en) * | 2019-12-13 | 2020-03-27 | 华中科技大学 | Lithium ion battery anode and preparation method thereof |
| CN112176771A (en) * | 2020-09-25 | 2021-01-05 | 柔电（武汉）科技有限公司 | Preparation method of lithium-philic carbon nanotube paper and preparation method of composite metal lithium cathode |
| CN112490433A (en) * | 2020-11-05 | 2021-03-12 | 中国电子科技集团公司第十八研究所 | Solid-state battery and method for improving rate capability and safety of solid-state battery |
| CN112885986A (en) * | 2021-01-29 | 2021-06-01 | 湖南美尼科技有限公司 | Positive pole piece for high-rate solid-state battery and preparation method |
| CN116741947A (en) * | 2023-06-01 | 2023-09-12 | 深圳市原速光电科技有限公司 | Preparation method and application of battery pole piece |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wei et al. | Uniform Li deposition by regulating the initial nucleation barrier via a simple liquid-metal coating for a dendrite-free Li–metal anode | |
| Wang et al. | Dendrite-free all-solid-state lithium batteries with lithium phosphorous oxynitride-modified lithium metal anode and composite solid electrolytes | |
| CN109980183A (en) | Method for improving cycle stability of anode for solid-state battery by atomic layer deposition treatment | |
| Zhang et al. | Building stable solid electrolyte interphases (SEI) for microsized silicon anode and 5V-class cathode with salt engineered nonflammable phosphate-based lithium-ion battery electrolyte | |
| Yang et al. | Surface restraint synthesis of an organic–inorganic hybrid layer for dendrite-free lithium metal anode | |
| CN105742713B (en) | All-solid-state polymer lithium battery | |
| Im et al. | Two-dimensional, P-doped Si/SiOx alternating veneer-like microparticles for high-capacity lithium-ion battery composite | |
| CN110085805B (en) | Composite anode and application thereof in solid polymer lithium ion battery | |
| CN104956530A (en) | Negative electrode for secondary battery and lithium secondary battery comprising same | |
| CN110783529B (en) | Lithium metal cathode for secondary battery and preparation and application thereof | |
| US20180316044A1 (en) | Method for producing a sodium-ion battery | |
| CN104904049A (en) | Anode for secondary battery and lithium secondary battery including same | |
| JP2018531497A6 (en) | Method for manufacturing sodium ion battery | |
| CN112490433A (en) | Solid-state battery and method for improving rate capability and safety of solid-state battery | |
| CN108475763A (en) | The method for preparing type lithium ion accumulator | |
| CN109428048B (en) | Method for producing negative electrode for aqueous lithium ion secondary battery and method for producing aqueous lithium ion secondary battery | |
| Cheng et al. | An in situ solidifying strategy enabling high-voltage all-solid-state Li-metal batteries operating at room temperature | |
| Raja et al. | High performance multi-functional trilayer membranes as permselective separators for lithium–sulfur batteries | |
| Qiu et al. | Growing nanostructured CuO on copper foil via chemical etching to upgrade metallic lithium anode | |
| CN112103512A (en) | Negative current collector, and preparation method and application thereof | |
| CN111164802A (en) | Negative electrode for lithium metal battery, method for producing the same, and lithium metal battery comprising the same | |
| Phiri et al. | Synergistic effect of a dual-salt liquid electrolyte with a LiNO3 functional additive toward stabilizing thin-film Li metal electrodes for Li secondary batteries | |
| Heng et al. | Organic salts with unsaturated bond and diverse anions as substrates for solid electrolyte interphase on graphite anodes | |
| Kang et al. | AgNO3-preplanted Li metal powder electrode: Preliminary formation of lithiophilic Ag and a Li3N-rich solid electrolyte interphase | |
| Naren et al. | Stabilizing Lithium Metal Batteries by Synergistic Effect of High Ionic Transfer Separator and Lithium–Boron Composite Material Anode |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190705 |
|
| WD01 | Invention patent application deemed withdrawn after publication |