CN113451658A - All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof - Google Patents
All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof Download PDFInfo
- Publication number
- CN113451658A CN113451658A CN202110772648.0A CN202110772648A CN113451658A CN 113451658 A CN113451658 A CN 113451658A CN 202110772648 A CN202110772648 A CN 202110772648A CN 113451658 A CN113451658 A CN 113451658A
- Authority
- CN
- China
- Prior art keywords
- solid
- lithium ion
- ion battery
- dimensional
- electrode material
- 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
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 63
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 239000006260 foam Substances 0.000 claims abstract description 46
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 45
- 239000007774 positive electrode material Substances 0.000 claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 claims abstract description 27
- 238000004070 electrodeposition Methods 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000000872 buffer Substances 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 24
- 229920002627 poly(phosphazenes) Polymers 0.000 claims description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- 239000010405 anode material Substances 0.000 claims description 13
- 239000010406 cathode material Substances 0.000 claims description 13
- 229920000767 polyaniline Polymers 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000002482 conductive additive Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 229910016233 LiMn1.42Ni0.42Co0.6O4 Inorganic materials 0.000 claims description 7
- 239000011324 bead Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 6
- XDMXNXNLJCQUHV-UHFFFAOYSA-N antimony;copper(1+) Chemical compound [Cu+].[Cu+].[Cu+].[Sb] XDMXNXNLJCQUHV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229910052493 LiFePO4 Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 229910007516 Li1.5Ni0.25Mn0.75O2.5 Inorganic materials 0.000 claims description 4
- 229910002993 LiMnO2 Inorganic materials 0.000 claims description 4
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000003431 cross linking reagent Substances 0.000 claims description 4
- 229910002096 lithium permanganate Inorganic materials 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000007787 solid Substances 0.000 abstract description 12
- 230000008901 benefit Effects 0.000 abstract description 6
- 229920000642 polymer Polymers 0.000 abstract description 6
- 230000002829 reductive effect Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 4
- 239000010949 copper Substances 0.000 description 19
- 239000000463 material Substances 0.000 description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 12
- 229910052744 lithium Inorganic materials 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 229910015645 LiMn Inorganic materials 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000007772 electrode material Substances 0.000 description 5
- -1 polyhexamethylene trichloride Polymers 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 229910018306 Cu2Sb Inorganic materials 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- 239000011244 liquid electrolyte Substances 0.000 description 4
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011267 electrode slurry Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 239000006173 Good's buffer Substances 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910016201 LiMn1.42Ni0.42Co0.16O4 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- BTVHBWGDJWUNKL-UHFFFAOYSA-N SC=1SC(=NN1)S.SC=1SC(=NN1)S Chemical compound SC=1SC(=NN1)S.SC=1SC(=NN1)S BTVHBWGDJWUNKL-UHFFFAOYSA-N 0.000 description 1
- XUGISPSHIFXEHZ-GPJXBBLFSA-N [(3r,8s,9s,10r,13r,14s,17r)-10,13-dimethyl-17-[(2r)-6-methylheptan-2-yl]-2,3,4,7,8,9,11,12,14,15,16,17-dodecahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C1C=C2C[C@H](OC(C)=O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 XUGISPSHIFXEHZ-GPJXBBLFSA-N 0.000 description 1
- 230000005856 abnormality Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000006138 lithiation reaction Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 150000002736 metal compounds Chemical group 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- IWXWFPGJAZUXBL-UHFFFAOYSA-N naphthalene-1,4-dione Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1.C1=CC=C2C(=O)C=CC(=O)C2=C1 IWXWFPGJAZUXBL-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
Images
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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application provides an all-solid-state lithium ion battery with a three-dimensional electrode structure and a preparation method thereof, wherein the all-solid-state lithium ion battery comprises an electrodeposition negative electrode material with a micro-nanometer level, is separated from a positive electrode material with a three-dimensional porous foam structure, and is characterized in that a polymer solid electrolyte is reduced onto the positive electrode material in a uniform and pinhole-free electrodeposition mode, and gaps of the porous foam structure are filled, so that compared with other types of lithium ion battery designs, the all-solid-state lithium ion battery can remarkably shorten the distance which lithium ions need to penetrate when the battery is charged/discharged, and the invention also describes a method for manufacturing the battery. Compared with the traditional solid lithium ion battery structure adopting the film technology, the solid lithium ion battery structure provided by the invention has the advantages that the three-dimensional structure can provide higher energy density, and the overall production mode of the electrodeposited negative electrode can effectively reduce the process complexity, reduce the production cost and improve the product quality and reliability.
Description
Technical Field
The invention relates to the field of lithium batteries, in particular to an all-solid-state lithium ion battery with a three-dimensional electrode structure and a manufacturing method thereof.
Background
Lithium is the lightest, positively charged ionic element and is therefore well suited for use in high energy density battery applications. Therefore, lithium ion batteries have become the most commonly used batteries in various portable electronic devices. The success of the electronics market has driven its adoption in Hybrid Electric Vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and electric vehicles (E-PHEVs)EV). In addition to these applications, the increasing demand for batteries to maintain extremely high charge and discharge current densities has prompted an increasing demand for more powerful portable electronic devices. Safety is also an important factor in the design of new lithium ion batteries, particularly in terms of transportation. Currently, most lithium batteries have a porous separator that is soaked in a solution containing LiPF6In the anhydrous carbonate-based electrolyte. These batteries are considerably liable to catch fire due to temperature abnormality and collision due to such an electrolytic solution, and therefore, all solid-state lithium batteries are an important direction for solving these problems.
Many studies have begun to try solid state lithium batteries as a safe alternative to conventional liquid electrolyte lithium batteries. However, before solid-state lithium-ion batteries are widely used in commercial applications, two major problems must be addressed. The first is that lithium ions diffuse relatively slowly into the positive and negative electrodes, and also diffuse slowly into the solid electrolyte separating the two electrodes, which makes the charge and discharge rates of such batteries lower than conventional lithium ion batteries. The second is the first result, because solid-state lithium ion batteries generally require complex industrially manufactured thin layers to compensate for slow solid-state diffusion, and expensive cost price must be paid to increase energy density, which is also a difficulty faced in current commercialization of all-solid-state lithium batteries.
While reducing the size of the electrode material may improve rate performance compared to large size materials, it is not easy to shorten the distance between the positive and negative battery structures, and lithium ions need to travel a large distance between macroscopically separated electrodes. The planar geometry of the cell significantly reduces the achievable energy density due to the limited common existing manufacturing techniques.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for manufacturing an all solid-state lithium ion battery having a three-dimensional electrode structure, a method for manufacturing a solid-state lithium ion battery having a shortened lithium ion diffusion path, in which a non-linear process is used to deposit uniform electrode and electrolyte layers.
In addition, the invention also provides an all-solid-state lithium ion battery with a three-dimensional electrode structure, which effectively improves the diffusion rate of lithium ions in the positive electrode and the negative electrode of the battery.
In order to realize one of the purposes, the invention adopts the technical scheme that: a preparation method of an all-solid-state lithium ion battery with a three-dimensional electrode structure comprises the following steps:
step 1: preparing a positive electrode material: mixing the anode slurry with the space bracket, and after the mixture is solidified, carrying out chemical etching treatment on the space bracket to form an anode material with a three-dimensional porous foam structure on the outer surface;
step 2: forming a solid electrolyte layer on the outer surface of the anode material in an electrodeposition mode, wherein the solid electrolyte layer is also positioned on the outer surface of the three-dimensional porous foam structure;
and step 3: forming a conductive compound buffer layer on the outer surface of the solid electrolyte layer in an electrodeposition mode;
and 4, step 4: the negative electrode material is formed in the three-dimensional porous foam structure in an electrodeposition mode and is electrically isolated from the positive electrode material through the solid electrolyte layer and the conductive compound buffer layer.
Further, the positive electrode slurry comprises a source positive electrode material, a carbon-based conductive additive and a binder.
Further wherein the source cathode material comprises LiCO2、LiMnO2、LiMn1.42Ni0.42Co0.6O4、Li1.5Ni0.25Mn0.75O2.5、LiNi0.5Mn1.5O4、LiFePO4And LiMnO4One or more of (a).
Further, the carbon-based conductive additive is graphite: the binder is polyvinylidene fluoride.
Further, the space frame is silica beads.
Further, the solid electrolyte layer is polyphosphazene. The polyphosphazene is specifically poly (hexachlorocyclotriphosphazene) which is subjected to crosslinking treatment by using a crosslinking agent 1,4-naphthoquinone, and the thickness of the solid electrolyte layer is 10 nm-1000 nm.
Further, the negative electrode material comprises one or more of nickel, copper antimonide or polyaniline.
In order to achieve the second object, the present application provides an all solid-state lithium ion battery with a three-dimensional electrode structure, comprising:
the surface of the anode material is provided with a plurality of three-dimensional porous foam structures;
a solid electrolyte layer coated onto an outer surface of the positive electrode material to provide relative resistance to current flow and lithium ion ride-through;
a conductive compound buffer layer coated on an outer surface of the solid electrolyte layer;
and the negative electrode material is filled in the three-dimensional porous foam structure on the surface of the positive electrode, and the negative electrode material and the positive electrode material are electrically isolated through the solid electrolyte layer and the conductive compound buffer layer.
The lithium ion battery further comprises a positive electrode collector and a negative electrode collector, wherein the positive electrode collector is electrically communicated with the positive electrode material, and the negative electrode collector is electrically communicated with the negative electrode.
The invention has the beneficial effects that: 1. by constructing the cathode material with a three-dimensional porous foam structure that enhances surface area compared to planar structures, high surface area to volume ratios can be achieved on the nano-and micro-scale. Porous foam structures with micro-nano scale or smaller features that reduce the lithium ion diffusion length within the electrode material and between the electrodes are advantageous in solid state lithium ion batteries because the conductivity of solid state electrolytes is typically significantly lower than that of conventional liquid electrolytes. Furthermore, unlike two-dimensional planar structures, cellular foam structures allow such distance reductions to be achieved while maintaining practical energy densities. Another benefit of using a porous foam structure is that it allows for a reduction in the amount of non-battery active materials present in the battery, such as current collectors, separators and packaging, which provides greater energy density than planar solid state batteries.
2. The positive electrode material is a three-dimensional porous foam and is separated from the negative electrode by a thin solid electrolyte, lithium ions from the positive electrode interpenetrate the negative electrode material through the solid electrolyte layer, allowing short lithium ion diffusion times within and between the electrode materials while maintaining useful energy density, and wherein multiple cells can be connected in parallel or in series to allow the capacity and voltage required for the application sought. Solid state lithium ion batteries have better safety characteristics than conventional lithium ion batteries and are not limited to low energy applications.
Drawings
Fig. 1 is a schematic cross-sectional view of an example of a three-dimensional porous foam structure on the surface of a positive electrode material according to the present invention.
Fig. 2 is a Scanning Electron Microscope (SEM) image of an example of a three-dimensional porous foam structure fabricated from the positive electrode material.
FIG. 3 is a synthetic LiMn doped with silicon (Si (IV))1.42Ni0.42Co0.16O4 nanoparticles, corresponding energy dispersive x-ray (EDS) spectra tested.
FIG. 4 is a synthetic LiMn1.42Ni0.42Co0.16O4Nanoparticles and electrodeposited Cu2Graph showing the cycle results of the voltage distribution of the full cell of Sb.
Fig. 5 is a schematic diagram of a specific application of the all-solid-state lithium ion battery of the present invention.
The reference numbers illustrate: a positive electrode material 10, a solid electrolyte layer 11, a conductive compound buffer layer 12, a negative electrode material 13, a positive electrode current collector 51, a negative electrode current collector 52, and a battery 53.
Detailed Description
Referring to fig. 1 to 5, the present invention relates to a method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure, including the following steps:
step 1: preparing a positive electrode material 10: mixing the anode slurry with the space bracket, and after the mixture is solidified, carrying out chemical etching treatment on the space bracket to form an anode material 10 with a three-dimensional porous foam structure on the outer surface;
step 2: forming a solid electrolyte layer 11 on the outer surface of the cathode material 10 by means of electrodeposition, wherein the solid electrolyte layer 11 is also positioned on the outer surface of the three-dimensional porous foam structure;
and step 3: forming a conductive compound buffer layer 12 on the outer surface of the solid electrolyte layer 11 by means of electrodeposition;
and 4, step 4: the negative electrode material 13 is formed in the three-dimensional porous foam structure by means of electrodeposition, and the negative electrode material 13 is electrically isolated from the positive electrode material 10 by the solid electrolyte layer 11 and the conductive compound buffer layer 12.
Wherein the method according to an embodiment of the present invention can be used to achieve high surface area to volume ratios on the nano-and micro-scale by constructing a positive electrode material 10 having a three-dimensional porous foam structure that enhances surface area compared to planar structures. Porous foam structures with micro-nano scale or smaller features that reduce the lithium ion diffusion length within the electrode material and between the electrodes are advantageous in solid state lithium ion batteries because the conductivity of solid state electrolytes is typically significantly lower than that of conventional liquid electrolytes. Furthermore, unlike two-dimensional planar structures, cellular foam structures allow such distance reductions to be achieved while maintaining practical energy densities. Another benefit of using a porous foam structure is that it allows for a reduction in the amount of non-battery active materials present in the battery, such as current collectors, separators and packaging, which provides greater energy density than planar solid state batteries.
Embodiments of the invention are briefly described in the drawings. Fig. 1 shows a lithium ion battery in the present application, which has a three-dimensional porous foam structure in a positive electrode material 10 coated with a solid electrolyte layer 11, a conductive compound buffer layer 12 coated outside the solid electrolyte layer 11, and a negative electrode material 13 filling the porous structure, thereby forming an interpenetrating electrode, and the overall process produces such a battery in an electrodeposition technique, resulting in a highly efficient and high-quality manufacturing method. All four components of the battery of the present invention: (1) a positive electrode material 10; (2) a solid electrolyte layer 11; (3) a conductive compound buffer layer 12; and (3) the anode material 13 is in a solid state.
The solid state lithium battery of the present invention has advantages over conventional liquid electrolyte lithium batteries, such as: reduced flammability, increased operating temperature range, and higher stability, thereby extending cycle and shelf life. The structure of the solid lithium battery increases the diffusion rate of lithium ions between the negative electrode and the positive electrode by reducing the diffusion path length of the lithium ions between the electrodes; this feature, in combination with the three-dimensional structure of the interpenetrating electrodes, allows the construction of high energy and power density batteries with long cycle and shelf life, as compared to two-dimensional planar geometries.
In the present invention, the cathode material 10 has a three-dimensional porous foam structure, such as a porous foam structure, which serves as a current collecting structure of the cathode material 10, and is covered by the solid electrolyte layer 11 with a conformal thin layer, the conductive compound buffer layer 12 is also covered by the solid dielectric layer with a conformal thin layer, and the conductive compound buffer layer 12 serves as a filling template for electrodeposition of the cathode material 13, filling the void space left in the previous step. The invention has the advantages that the positive electrode and the negative electrode are staggered or interpenetrated on the porous metal foam electrode, and the three-dimensional structure allows lithium ions to diffuse in the electrode material and between the electrodes at short distance, and simultaneously, the practical energy density is maintained.
Further, the positive electrode slurry comprises a source positive electrode material 10, a carbon-based conductive additive and a binder.
Further wherein the source cathode material 10 comprises LiCO2、LiMnO2、LiMn1.42Ni0.42Co0.6O4、Li1.5Ni0.25Mn0.75O2.5、LiNi0.5Mn1.5O4、LiFePO4And LiMnO4One or more of (a).
Further, the negative electrode material 13 includes one or more of nickel, copper antimonide, or polyaniline.
Further, the carbon-based conductive additive is graphite: the binder is polyvinylidene fluoride. Further, the space frame is silica beads.
The invention as shown in fig. 1, embodiments of the invention are used in positive electrode porous foam structures, which may be made of materials including, but not limited to, LiCO2、LiMnO2、LiMn1.42Ni0.42Co0.6O4、Li1.5Ni0.25Mn0.75O2.5、LiNi0.5Mn1.5O4、LiFePO4And LiMnO4And 2,5-dimercapto-1,3,4-thiadiazole (2,5-dimercapto-1,3, 4-thiadiazole); and the negative electrode material 13 may be made of nickel (Ni), copper (Cu), copper antimonide (Cu), or the like2Sb) one of conductive materials or a composite material.
The following specific preparation methods of the positive electrode material 10 are specifically listed:
the porosity and structure of the porous foam of the positive electrode material 10 can be controlled by the space frame used (e.g., silica beads (SiO)2) Size and shape). The space holder (e.g., silica beads (SiO) is initially mixed with the positive slurry2) Voltage can be measured after the positive electrode slurry is dried, when Cu is present2Sb as negative electrode material 13, LiCoO2For the positive electrode material 10, the voltage should be about 300 mV. In addition, the internal resistance measured using a digital multimeter should be at 106And omega is about. At this point a preliminary curing step is performed followed by the application of HF solution to the Silica (SiO)2) The beads are chemically etched away to form the positive electrode material 10 having a three-dimensional porous foam structure.
Meanwhile, LiCO can be used as the positive electrode material 10 slurry2(99.8％，Aldrich)、LiFePO4(99.5％，MTI)、LiMn1.42Ni0.42Co0.6O4And the like, and using particulate graphite as a carbon-based conductive additive for the electrode. Each material was ball milled in a planetary ball mill fitted with an alumina ceramic shell and grinding balls. Typically, 10 ml of isopropanol, 5 grams of material and 4 ceramic grinding balls were placed in a ceramic housing, spun at 240 rpm for 30 minutes, and then paused for 30 minutes to dissipate heat. Repeat 24 times. This process reduces the particle size to below 500 nm. After ball milling, the positive electrode material 10, the carbon-based conductive additive and the binder are combined together, and the compositions of the positive electrode material, the carbon-based conductive additive and the binder are 82%, 10% and 8% respectively. Triethyl Phosphate (Triethyl Phosphate) was then added to the combined weight of the positive electrode, conductor and binder1.5 times, and stirring until the adhesive is completely dissolved. The viscosity of the slurry can be adjusted using the increase or decrease of triethyl phosphate. The triethyl phosphate (triethyl phosphate) was chosen because it did not damage the electrodeposited solid electrolyte layer 11 polyphosphazene (PPZ).
Referring to fig. 2, a Scanning Electron Microscope (SEM) image of an example of the positive electrode material 10 fabricated into a three-dimensional porous foam structure is shown, which is a low-magnification SEM image of the positive electrode in which micrometer-sized pillars are clearly visible and shorter-sized pillars of the three-dimensional porous foam structure can be observed.
LiMn was used in the present example1.42Ni0.42Co0.6O4For the positive electrode, studies on electrochemical properties were conducted in lithium ion batteries. In the use of space scaffold silica beads (SiO)2) LiMn was measured1.42Ni0.42Co0.6O4Doped with Si (IV), as shown in FIG. 3 for synthetic LiMn doped with silicon (Si (IV))1.42Ni0.42Co0.6O4Nanoparticles, corresponding energy dispersive x-ray (EDS) spectra tested, demonstrate the presence of the elemental components manganese, nickel, cobalt and silicon. LiMn can be added into nano particles by adding Si (IV)1.42Ni0.42Co0.6O4The nano particles achieve the effect of modification and avoid the original unmodified LiMn1.42Ni0.42Co0.6O4The nanoparticles experienced an observable capacity fade during the first few cycles and continued capacity fade with increasing cycle times.
Example electrochemical performance of the material was tested, and it was shown in fig. 4 that the complete solid-state full cell includes a positive electrode material 10, a solid electrolyte layer 11, a conductive compound buffer layer 12, and a negative electrode material 13, and the cycle results of voltage distribution of the resulting full cell were tested, with an average value of 3.7V; in fig. 4, the positive electrode material 10 includes PVDF, graphite, LiMn1.42Ni0.42Co0.6O4A nanoparticle; wherein the solid electrolyte layer 11 is PPZ; electrodeposited Cu2Sb was used as the negative electrode material 13. The full cell has a discharge potential with an average value of about 3.7V, which is the same potential level as that of a conventional Li-ion battery.
Further, the solid electrolyte layer 11 is polyphosphazene. The polyphosphazene is specifically polyhexamethylene trichloride which is subjected to crosslinking treatment by using a crosslinking agent 1,4-naphthoquinone, and the thickness of the solid electrolyte layer 11 is 10 nm-1000 nm.
In the present invention, the solid electrolyte layer 11 has properties advantageous to a lithium ion battery. These properties include, but are not limited to, long cycle life, long shelf life, reduced fire hazard, high operating temperatures and less stringent packaging requirements compared to liquids. This structure is different from the solid state electrolytes proposed in current reports, including ceramics, polymers or composites, which are generally incorporated into two-dimensional planar batteries. The invention electrodeposits a solid electrolyte layer 11 polyphosphazene (PPZ) on a three-dimensional porous foam structure of a positive electrode material 10, more precisely, a cross-linked polyhexamethylene chlorotrifluorosphazene is used, and the cross-linking agent used comprises 1,4-naphthoquinone (1, 4-naphthoquinone). A polyphosphazene film is electrodeposited on a porous foam positive electrode having a high specific surface area. As the surface is gradually blocked by the insulating PPZ layer, the charge passed during the reductive scan is greatly reduced. After 30 potential scans, 36 times at 0.85 and-1.3V with Ag/Ag+In between, the charge passed during the reduction scan was reduced by a factor of 20 and showed little change with further scanning, indicating that the surface was completely coated. Although not visible to the naked eye, PPZ-coated porous foam and electrodeposited porous foam positive electrodes showed a slight increase in mechanical stiffness. The morphology of the PPZ layer deposited on the planar anode substrate by electrodeposition was observed by an Atomic Force Microscope (AFM), and the result showed that the thickness of the PPZ layer was about 400 nm. The preferred thickness for the organic polymer electrolyte layer of the complete cell embodiments of the present invention is in the range between about 10nm and about 1000nm, with a more preferred thickness in the range between about 25nm and 500nm, and with an optimal thickness in the range between about 50nm and 250nm thick.
Several possible materials may be electrodeposited to form solid-state electrolytes that meet these requirements, including but not limited to polyphosphazenes (PPZ). Polyphosphazene polymers have a wide variety of materials for industrial applications, including a material with essentially repetitive elasticity, with side chains in the main chain, andcustomized to the particular application. In general, such polymers have excellent chemical resistance to organic solvents and are also good flame retardants. For example: poly [ bis (2- (2-methoxy-ethoxy) phosphazene]The lithium ion with the highest salt content in the polymer dry electrolyte reaches the conductivity (10)-5Scm-1)。
In the embodiment of the present invention, as shown in fig. 1, between the solid electrolyte layer 11 and the anode material 13, a conductive compound buffer layer 12 is added. The conductive compound buffer layer 12 may use a conductive polymer such as, but not limited to, polyaniline (polyaniline) used. The addition of the conductive compound buffer layer 12 has several advantages: (1) the strength of the solid electrolyte membrane is compensated, and the conductive compound buffer layer 12 can increase the structural strength of the solid electrolyte membrane due to the problems of expansion and contraction of heat and cold, expansion of materials and the like during the operation of the battery; (2) the porous foam micro-gap is effectively filled, and the solid electrolyte layer 11 polyphosphazene (PPZ) and polyaniline (polyaniline) have good organic affinity and can be effectively immersed in the micro-gap; (3) an effective conductive layer is formed, polyaniline (polyaniline) has good conductivity, and a polymer of the polyaniline is of a three-dimensional net structure, so that formation of lithium crystal branches is avoided; (4) the carrier for the electrodeposition of the negative electrode material 13 is formed, the negative electrode material 13 is nickel (Ni), copper (Cu) or copper antimonide (Cu2Sb), the subsequent electrodeposition is carried out on the carrier to form the negative electrode, polyaniline (polyanaline) has good elasticity, and when the negative electrode expands or contracts, the polyaniline can be used as a good buffer material to avoid the deformation of the whole material.
Specific filling methods of the negative electrode material 13 are as follows:
the embodiments of the present invention describe crystalline copper antimonide (Cu) directly electrodeposited onto the conductive compound buffer layer 12 from an aqueous solution at room temperature2Sb) film. From a mixture containing 0.025M antimony (III) oxide (Sb)2O3Nanopowder, 99.9% or more, Aldrich) and 0.08M aqueous solution of copper (II) nitrate in 0.4M citric acid (H)3Cit, 99.5% or more, Aldrich) in Cu2And (5) an Sb film. Copper nitrate Cu (NO)3)299.9% or more, Aldrich) by adding citric acid to Millipore high purity water (18M Ω) and then adding Sb2O3Assisted by mechanical agitation of Sb2O3Is completely dissolved, then Cu (NO) is added3)2. The pH was then raised to 6 by the addition of 5M potassium hydroxide (KOH, ACS certified, Fisher). Cu2The Sb thin film is obtained by electrodeposition on the conductive compound buffer layer 12 at 50 ℃, with a potential of-1.05V, relative to SSCE. Deposition controllable Cu by changing deposition time2The thickness of Sb. In this example Cu was electrodeposited2Sb can be followed by electrodeposition of metal elements for support and wiring (not limited to copper or nickel). By varying Cu (NO) in the deposition solution3)2And by applying different deposition potentials, or by adding Ni (NO) to the deposition solution3)2To perform electrodeposition of nickel. Examples Cu2Sb can be directly deposited on a conductive substrate, the composition and thickness are precisely controlled under mild conditions, a complex shape is formed and enters deep recesses, excellent electrical contact is achieved, and post-annealing is not required. This allows Cu2Sb is electrodeposited onto or as the conductive three-dimensional porous foam.
Embodiments provide the ability to control the pore size of the struts in the three-dimensional porous foam structure in the positive electrode material 10 to maximize cycle performance and allow optimization of the properties of the final battery at power and energy density. In this embodiment, the porous foam struts are entirely lithium ion active material and no lithium ion inactive material is present. The absence of such inactive materials in the electrode affects the energy and power density of the battery because the mass of the electrode has a higher activity for the incorporation of lithium ions, particularly with Cu in this embodiment2Sb is a metal compound and does not undergo a large volume change during charge and discharge. Negative electrode Material 13 (not limited to Cu)2Sb, copper, or nickel) exhibits excellent performance in lithium ion batteries upon lithiation: (1) increased charge storage capacity; (2) increased charge/discharge rates; and (3) reducing detrimental metals of the plated lithium on the negative electrode. The electrochemical deposition of the negative electrode material 13 exhibits a high surface area in the porous foam while maintaining excellent electrical contact with the porous foam. Electrodeposition of cathode Material 1The thickness of 3 may be in the range of about 50nm to about 10um, more preferably between about 200nm and about 5um, and optimally between about 500nm and about 3um, as controlled by the deposition parameters employed. Control of the thickness is beneficial because it allows for optimization of the cycling performance of the anode material 13 and provides a means for lithium ion capacity of the cathode material 10.
Also, the present invention provides an all solid-state lithium ion battery having a three-dimensional electrode structure, including: the positive electrode material 10 is characterized in that the surface of the positive electrode material 10 is provided with a plurality of three-dimensional porous foam structures; a solid electrolyte layer 11 coated on an outer surface of the cathode material 10 to provide relative resistance to current and lithium ion crossover; a conductive compound buffer layer 12 coated on an outer surface of the solid electrolyte layer 11; and the negative electrode material 13 is filled in the three-dimensional porous foam structure on the surface of the positive electrode, and the negative electrode material 13 is electrically isolated from the positive electrode material 10 through the solid electrolyte layer 11 and the conductive compound buffer layer 12.
Further, the device also comprises a positive electrode collector and a negative electrode collector, wherein the positive electrode collector is electrically communicated with the positive electrode material 10, and the negative electrode collector is electrically communicated with the negative electrode material 13.
As shown in fig. 5, a positive electrode current collector 51 is attached to the positive electrode material 10. The positive current collector 51 comprises a conductive metal, such as, but not limited to, aluminum, in the form of a thin foil or a grid, the positive current collector 51 being attached to a positive electrode material 10 (e.g., LiMn)1.42Ni0.42Co0.16O4) (ii) a To improve the conductivity of the anode, an anode current collector 52 may be wound around the filled anode material 13 to complete the anode material 13 contact on the top and sides of the three-dimensional structure. Once this is achieved, the entire assembly completes the manufacture of a complete lithium ion battery having interpenetrating negative and positive electrodes. The voltage drop may be measured between the lead connected to the negative current collector 52 and the lead of the positive current collector 51 using a voltage measuring device. This position may also be used to connect an external load to draw current from the battery 53, or to connect the positive and negative poles of the battery 53 to the battery 53 in order to charge the battery 53.
The above embodiments are merely illustrative of the preferred embodiments of the present invention, and not restrictive, and various changes and modifications to the technical solutions of the present invention may be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are intended to fall within the scope of the present invention defined by the appended claims.
Claims (10)
1. A preparation method of an all-solid-state lithium ion battery with a three-dimensional electrode structure is characterized by comprising the following steps:
step 1: preparing a positive electrode material: mixing the anode slurry with the space bracket, and after the mixture is solidified, carrying out chemical etching treatment on the space bracket to form an anode material with a three-dimensional porous foam structure on the outer surface;
step 2: forming a solid electrolyte layer on the outer surface of the anode material in an electrodeposition mode, wherein the solid electrolyte layer is also positioned on the outer surface of the three-dimensional porous foam structure;
and step 3: forming a conductive compound buffer layer on the outer surface of the solid electrolyte layer in an electrodeposition mode;
and 4, step 4: the negative electrode material is formed in the three-dimensional porous foam structure in an electrodeposition mode and is electrically isolated from the positive electrode material through the solid electrolyte layer and the conductive compound buffer layer.
2. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 1, wherein: the anode slurry comprises a source anode material, a carbon-based conductive additive and a binder.
3. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 2, wherein: wherein the source cathode material comprises LiCO2、LiMnO2、LiMn1.42Ni0.42Co0.6O4、Li1.5Ni0.25Mn0.75O2.5、LiNi0.5Mn1.5O4、LiFePO4And LiMnO4One or more of (a).
4. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 2, wherein: the carbon-based conductive additive is graphite: the binder is polyvinylidene fluoride.
5. The method for producing an all-solid-state lithium ion battery having a three-dimensional electrode structure according to any one of claims 1 to 4, wherein: the space frame is silica beads.
6. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 1, wherein: the solid electrolyte layer is polyphosphazene.
7. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 6, wherein: the polyphosphazene is specifically poly (hexachlorocyclotriphosphazene) which is subjected to crosslinking treatment by using a crosslinking agent 1,4-naphthoquinone, and the thickness of the solid electrolyte layer is 10 nm-1000 nm.
8. The method for manufacturing an all-solid-state lithium ion battery with a three-dimensional electrode structure according to claim 1, wherein: the negative electrode material comprises one or more of nickel, copper antimonide or polyaniline.
9. An all-solid-state lithium ion battery of a three-dimensional electrode structure, comprising:
the surface of the anode material is provided with a plurality of three-dimensional porous foam structures;
a solid electrolyte layer coated onto an outer surface of the positive electrode material to provide relative resistance to current flow and lithium ion ride-through;
a conductive compound buffer layer coated on an outer surface of the solid electrolyte layer;
and the negative electrode material is filled in the three-dimensional porous foam structure on the surface of the positive electrode, and the negative electrode material and the positive electrode material are electrically isolated through the solid electrolyte layer and the conductive compound buffer layer.
10. The all-solid-state lithium ion battery of a three-dimensional electrode structure according to claim 9, characterized in that: the cathode collector is electrically communicated with the cathode material, and the cathode collector is electrically communicated with the cathode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772648.0A CN113451658A (en) | 2021-07-08 | 2021-07-08 | All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110772648.0A CN113451658A (en) | 2021-07-08 | 2021-07-08 | All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113451658A true CN113451658A (en) | 2021-09-28 |
Family
ID=77815637
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110772648.0A Pending CN113451658A (en) | 2021-07-08 | 2021-07-08 | All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113451658A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114552023A (en) * | 2021-11-02 | 2022-05-27 | 万向一二三股份公司 | Laminated all-solid-state battery with self-supporting structure |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125024A1 (en) * | 2010-04-05 | 2011-10-13 | Ecole Polytechnique Federale De Lausanne (Epfl) | Improved electrode |
| CN103947021A (en) * | 2011-08-02 | 2014-07-23 | 普列托电池公司 | Lithium-ion battery having interpenetrating electrodes |
| US20170294678A1 (en) * | 2016-04-11 | 2017-10-12 | Samsung Electronics Co., Ltd. | Composite solid electrolyte, protected anode and lithium battery including the same, and method of preparing the composite solid electrolyte |
| CN107369813A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | Metal lithium electrode and preparation method thereof, lithium metal second electrode negative pole, battery |
| US20170365877A1 (en) * | 2014-12-29 | 2017-12-21 | Seoul National University R&Db Foundation | All-solid ion battery |
| CN107834078A (en) * | 2017-09-27 | 2018-03-23 | 山西大学 | A kind of exotic atom adulterates cellular porous carbon material and preparation method thereof |
| CN110386827A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院金属研究所 | A kind of reverse foamed material and its preparation method and application |
| CN112271325A (en) * | 2020-09-15 | 2021-01-26 | 赖见 | Three-dimensional solid-state lithium battery and preparation method thereof |
| WO2021118459A1 (en) * | 2019-12-12 | 2021-06-17 | National University Of Singapore | Porous composites, scaffolds, foams, methods of fabrication and uses thereof |
-
2021
- 2021-07-08 CN CN202110772648.0A patent/CN113451658A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011125024A1 (en) * | 2010-04-05 | 2011-10-13 | Ecole Polytechnique Federale De Lausanne (Epfl) | Improved electrode |
| CN103947021A (en) * | 2011-08-02 | 2014-07-23 | 普列托电池公司 | Lithium-ion battery having interpenetrating electrodes |
| US20170365877A1 (en) * | 2014-12-29 | 2017-12-21 | Seoul National University R&Db Foundation | All-solid ion battery |
| US20170294678A1 (en) * | 2016-04-11 | 2017-10-12 | Samsung Electronics Co., Ltd. | Composite solid electrolyte, protected anode and lithium battery including the same, and method of preparing the composite solid electrolyte |
| CN107369813A (en) * | 2016-05-12 | 2017-11-21 | 华为技术有限公司 | Metal lithium electrode and preparation method thereof, lithium metal second electrode negative pole, battery |
| CN107834078A (en) * | 2017-09-27 | 2018-03-23 | 山西大学 | A kind of exotic atom adulterates cellular porous carbon material and preparation method thereof |
| CN110386827A (en) * | 2018-04-16 | 2019-10-29 | 中国科学院金属研究所 | A kind of reverse foamed material and its preparation method and application |
| WO2021118459A1 (en) * | 2019-12-12 | 2021-06-17 | National University Of Singapore | Porous composites, scaffolds, foams, methods of fabrication and uses thereof |
| CN112271325A (en) * | 2020-09-15 | 2021-01-26 | 赖见 | Three-dimensional solid-state lithium battery and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114552023A (en) * | 2021-11-02 | 2022-05-27 | 万向一二三股份公司 | Laminated all-solid-state battery with self-supporting structure |
| CN114552023B (en) * | 2021-11-02 | 2023-07-07 | 万向一二三股份公司 | Laminated all-solid-state battery with self-supporting structure |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6367390B2 (en) | Production of large capacity prism lithium ion alloy anode | |
| JP6280865B2 (en) | Lithium ion battery with interpenetrating electrodes | |
| KR101103841B1 (en) | Metal ions-assisted electroless etching method for the bundle type silicon nano-rod composite and its application as anode materials for lithium secondary batteries | |
| EP2839529B1 (en) | Alkali and alkaline-earth ion batteries with hexacyanometallate cathode and non-metal anode | |
| US9312540B2 (en) | Conformal coating on nanostructured electrode materials for three-dimensional applications | |
| US8852804B2 (en) | Negative electrode for lithium ion secondary battery and lithium ion secondary battery including the same | |
| KR20210007273A (en) | Composite anode active material, and Anode and Lithium secondary battery comprising the same | |
| KR102635072B1 (en) | Negative active material for lithium secondary battery, method of manufacturing the same, and lithium secondary battery including the same | |
| KR101817418B1 (en) | Negative electrode active material and method for preparing the same | |
| US8563178B2 (en) | Negative electrode for lithium secondary battery including a multilayer film on a tin based current collector and manufacturing method thereof | |
| Zhang et al. | A 10‐μm Ultrathin Lithium Metal Composite Anodes with Superior Electrochemical Kinetics and Cycling Stability | |
| CN113451658A (en) | All-solid-state lithium ion battery with three-dimensional electrode structure and manufacturing method thereof | |
| JP2014519143A (en) | Lithium ion battery electrode | |
| WO2017177960A1 (en) | Electrolyte solution, battery, and battery pack | |
| CN108539151B (en) | Electrode material for secondary battery and secondary battery | |
| US20160049651A1 (en) | Negative electrode for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery | |
| WO2014156068A1 (en) | Negative electrode for non-aqueous electrolyte secondary batteries and non-aqueous electrolyte secondary battery | |
| CN116504930A (en) | Negative electrode for secondary battery, method for manufacturing negative electrode, and secondary battery comprising same | |
| CN114665060A (en) | Electrode structure, positive electrode and electrochemical device including the same, and method of manufacturing the same | |
| JP6284492B2 (en) | Anode for non-aqueous electrolyte secondary battery and non-aqueous electrolyte secondary battery | |
| Sharma et al. | Zeolite Coated Separators for Improved Performance and Safety of Lithium Metal Batteries | |
| Ha et al. | Electrochemical properties of electrode comprising of Si nanopowder inserted in an enclosed structure in C-Coated AAO by using a facile method | |
| Dominguez | Strategies To Improve The Electrochemical Of Performance Transition Metal Compounds As Anode Materials For Li-Ion Batteries | |
| Ruiz | Strategies to Improve The Electrochemical of Performance Transition Metal Compounds as Anode Materials for Li-Ion Batteries | |
| KR20230063958A (en) | Negative Electrode for Secondary Battery, Secondary Battery Comprising the Same and Manufacturing Method Thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210928 |
|
| RJ01 | Rejection of invention patent application after publication |