CN114613944B - Method for preparing solid-state battery electrode through microwave process - Google Patents
Method for preparing solid-state battery electrode through microwave process Download PDFInfo
- Publication number
- CN114613944B CN114613944B CN202210300487.XA CN202210300487A CN114613944B CN 114613944 B CN114613944 B CN 114613944B CN 202210300487 A CN202210300487 A CN 202210300487A CN 114613944 B CN114613944 B CN 114613944B
- Authority
- CN
- China
- Prior art keywords
- microwave
- electrode
- lithium
- wave
- battery electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000011358 absorbing material Substances 0.000 claims abstract description 16
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011149 active material Substances 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 11
- 239000006258 conductive agent Substances 0.000 claims abstract description 11
- 238000012545 processing Methods 0.000 claims abstract description 11
- 239000011812 mixed powder Substances 0.000 claims abstract description 9
- 238000005507 spraying Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000654 additive Substances 0.000 claims abstract description 6
- 230000000996 additive effect Effects 0.000 claims abstract description 6
- 239000013543 active substance Substances 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- 239000002861 polymer material Substances 0.000 claims description 7
- 238000003825 pressing Methods 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- -1 lithium hexafluoroarsenate Chemical compound 0.000 claims description 6
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 5
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 0.000 claims description 5
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 238000000462 isostatic pressing Methods 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 239000007784 solid electrolyte Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 238000005229 chemical vapour deposition Methods 0.000 claims description 2
- 238000000975 co-precipitation Methods 0.000 claims description 2
- 238000003618 dip coating Methods 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- 238000001513 hot isostatic pressing Methods 0.000 claims description 2
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 238000005240 physical vapour deposition Methods 0.000 claims description 2
- 229920000767 polyaniline Polymers 0.000 claims description 2
- 229920005596 polymer binder Polymers 0.000 claims description 2
- 239000002491 polymer binding agent Substances 0.000 claims description 2
- 229920000128 polypyrrole Polymers 0.000 claims description 2
- 229920000123 polythiophene Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 238000003746 solid phase reaction Methods 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims 1
- 239000004642 Polyimide Substances 0.000 claims 1
- 239000004721 Polyphenylene oxide Substances 0.000 claims 1
- 229920002492 poly(sulfone) Polymers 0.000 claims 1
- 229920002647 polyamide Polymers 0.000 claims 1
- 229920000728 polyester Polymers 0.000 claims 1
- 229920000570 polyether Polymers 0.000 claims 1
- 229920001721 polyimide Polymers 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 8
- 238000001035 drying Methods 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 8
- 230000007547 defect Effects 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 7
- 239000011888 foil Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007790 scraping Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000005019 vapor deposition process Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- VOEUMFXKYRCDKK-UHFFFAOYSA-N FS(=N)F.FS(=N)F.[Li] Chemical compound FS(=N)F.FS(=N)F.[Li] VOEUMFXKYRCDKK-UHFFFAOYSA-N 0.000 description 1
- 229910015013 LiAsF Inorganic materials 0.000 description 1
- 229910013075 LiBF Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a method for preparing a solid-state battery electrode by a microwave process, which comprises the following steps: (1) coating the wave-absorbing material outside the active substance; (2) Uniformly mixing the active material with the core-shell structure, the conductive agent and the additive to obtain electrode mixed powder; the electrode mixed powder obtained in the step (3) is pressed into a film; (4) And (5) putting the film into a special microwave die, and then performing microwave processing to generate the battery electrode. The invention obtains the positive electrode precursor through the spraying process, so that the microwave absorbing material used as the binder is uniformly distributed, the particles are well coated, the electrode is compact and the components are more uniform at the same time through the subsequent microwave processing, and the defects and limitations of the traditional dry process can be overcome.
Description
Technical Field
The invention belongs to the technical field of secondary battery electrode materials, and particularly relates to a method for preparing a solid-state battery electrode through a microwave process.
Background
The organic liquid electrolyte in the traditional lithium ion battery has great potential safety hazard caused by inflammability. The thermal runaway risk of the all-solid-state lithium battery is far lower than that of the traditional lithium ion battery, and lithium dendrites generated by the negative electrode in the charge and discharge process can be effectively blocked due to good mechanical property of the electrolyte, so that dead lithium is reduced, the cycle life of the battery is prolonged, and the energy density of the battery is improved, so that the development of the all-solid-state battery becomes an important direction for developing a new generation of energy storage technology.
The solid electrode is used as the core component of the all-solid battery, and the main problem existing at present is that the gaps among active substances, conductive agents and solid electrolyte particles in the electrode are larger, a large number of point-to-point contacts exist, so that a large interfacial resistance exists among the solid particles, and the transmission of lithium ions in the electrode is limited, thereby weakening the rate performance and capacity performance of the battery. Thus, the preparation of a dense and high ionic conductivity positive electrode is one of the bottlenecks in the development of all-solid-state batteries.
The commercial solid-state battery positive electrode is mostly prepared by a wet coating process, wherein the wet process is to uniformly mix a binder with an active material and a conductive agent in a liquid phase after the binder is fully dissolved or dispersed in a solvent, and then to obtain the positive electrode by drying and volatilizing the solvent after the slurry is coated. The wet process is widely used in lithium battery factories, the binder is uniformly dispersed, and the binding effect is good, but the defects of insufficient environment protection, high cost, poor conductivity, easy cracking of thick pole pieces, side reaction of residual solvent and the like exist in the use of solvents (such as NMP). The electrode plate with large porosity is left after the solvent volatilizes, so that the interface resistance is large, the lithium ion conductivity is poor, and further the problems of the rate performance and the capacity performance of the battery are caused.
In contrast, the dry process is simple, and has the advantage of reducing voids without the need for solvents. There are many technical routes for dry electrodes, among which the most mature technologies available from Maxwell corporation, specifically include the following: mixing active material, conductive agent and Polytetrafluoroethylene (PTFE) in a mixer, extruding the powder mixture to form a continuous self-supporting electrode film, and finally pressing the thin electrode and the current collector together to form the battery pole piece. The traditional dry process has the defect that each component is not easy to disperse in a polymer melt, so that the obtained electrode film has internal verification phase separation and poor mechanical property. Meanwhile, the dry electrode needs long-time hot rolling or extrusion hot processing, has high energy consumption and is easy to cause thermal degradation of materials such as polymers. It is therefore highly desirable to develop a process that solves the above-mentioned problems.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a method for preparing a solid-state battery electrode by a microwave process. The anode precursor is obtained through a spraying process, so that the microwave absorbing material serving as a binder is uniformly distributed, particles are well coated, and the components are more uniform while the electrode is compact through subsequent microwave processing, so that the defects and limitations of the traditional dry process can be overcome.
In order to achieve the above object, one of the technical solutions of the present invention is a method for preparing a solid-state battery electrode by a microwave process, specifically comprising the steps of:
(1) Coating the wave-absorbing material outside the active substance;
(2) Uniformly mixing the active material with the core-shell structure formed in the step (1) with a conductive agent and an additive to obtain electrode mixed powder;
(3) Pressing the electrode mixed powder obtained in the step (2) into a film;
(4) And (3) putting the film prepared in the step (3) into a special microwave die, and then carrying out microwave processing, wherein a wave-absorbing melting reaction occurs in the electrode, so that a compact electrode is generated.
In a preferred embodiment of the present invention, the coating process in the step (1) is a spraying process or a vapor deposition process.
In a preferred embodiment of the present invention, the wave-absorbing material in the step (1) includes one or more of a wave-absorbing carbon material, an iron-based wave-absorbing material, a wave-absorbing ceramic material, and a wave-absorbing polymer material.
Further, the wave-absorbing carbon material is preferably conductive graphite, graphene, carbon nanotubes and carbon fibers, the iron-based wave-absorbing material is preferably ferrite, the wave-absorbing ceramic material is preferably silicon carbide and silicon nitride, and the wave-absorbing polymer material is preferably an organic substance containing polar functional groups, such as polyaniline, polyethylene glycol, polythiophene, polypyrrole and the like.
Still further, the wave-absorbing polymeric material may be doped with a lithium salt prior to use, including tetrafluoroboric acid (LiBF) 4 ) Lithium perchlorate (LiClO) 4 ) Lithium hexafluoroarsenate (LiAsF) 6 ) Lithium hexafluorophosphate
(LiPF 6 ) One or more of lithium bisoxalato borate (LiBOB), lithium difluorooxalato borate (LiDFOB), lithium bisdifluorosulfimide (LiFSI) and lithium bistrifluoromethylsulfonimide (LiTFSI).
Still further, the wave-absorbing polymer material is preferably at least one of polyethylene glycol and derivatives thereof.
Further, the lithium salt is preferably lithium perchlorate (LiClO) 4 ) Or lithium bis (trifluoromethylsulfonyl) imide (LiTFSI).
Further, the mass ratio of the lithium salt to the wave-absorbing polymer material is 0.01-0.8:1.
In a preferred embodiment of the present invention, the ion conductivity of the wave-absorbing material in the step (1) is 10-10-10-1S/cm.
In a preferred embodiment of the present invention, the active material in the step (1) includes one or more of lithium iron phosphate, lithium cobalt oxide, lithium manganate, ternary cathode materials and derivatives thereof, elemental sulfur, sulfur-containing compounds and derivatives thereof, and organic materials and derivatives thereof having redox activity.
In a preferred embodiment of the present invention, the coating method in the step (1) includes a mechanical mixing method, a solid phase reaction method, a physical and chemical vapor deposition method, a dip coating method, a sol-gel method, a hydrothermal method, a co-precipitation method, an electrodeposition method, a ball milling method, a spray coating method, a microwave method, and an electrostatic spraying method.
In a preferred embodiment of the present invention, the thickness of the coating layer in the step (1) is 1nm-1cm.
In a preferred embodiment of the present invention, the mass fraction of the wave-absorbing material in the electrode mixed powder in the step (2) is 0.1% -90%.
In a preferred embodiment of the present invention, the conductive agent in the step (2) is one or more of carbon black, conductive graphite, ketjen black, super P, carbon fiber, carbon nanotube, and graphene.
In a preferred embodiment of the present invention, the additive in the step (2) is one or more of a polymer binder, a solid electrolyte and an electrolyte.
In a preferred embodiment of the present invention, the pressing in the step (3) is performed by vacuum hot pressing, atmosphere hot pressing, isostatic pressing, hot isostatic pressing, reactive hot pressing, vibration hot pressing, isostatic pressing, or ultra-high pressure sintering.
In a preferred embodiment of the present invention, the pressing in the step (3) is performed at a pressure of 0.1-3000MPa and a temperature of 30-1500 ℃.
In a preferred embodiment of the present invention, the film thickness of the pressed film in the step (3) is 5nm to 1cm.
In a preferred embodiment of the present invention, the microwave in the step (4) is an electromagnetic wave with a frequency ranging from 300MHz to 300GHz, the microwave heating is performed at a frequency ranging from 300MHz to 300GHz, and the wave may be in the form of sine wave, cosine wave, square wave, transverse wave, longitudinal wave, or any combination thereof.
In a preferred embodiment of the present invention, the microwave power in the step (4) is 10-9000W, and the microwave time is 0.01-3600S.
In order to achieve the above object, a second aspect of the present invention is a solid-state battery electrode obtained by a method for producing a solid-state battery electrode by a microwave process.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
1. the method can lead the microwave absorbing material used as the binder to be evenly distributed, thereby better coating the particles; the selected conductive agent not only plays a role in improving the electronic conductivity, but also has better wave absorbing performance; the fully dried powder can be in closer contact with the components through pressure, so that the electrode density is improved, the thick electrode can be prepared, the cycle performance is improved, and the service life of the battery is prolonged;
2. compared with the wet process, the method of the invention has the advantages that the powder is subjected to pressure treatment, so that the problem of poor contact between particles in the electrode is solved;
3. compared with the traditional dry method, the method can achieve better binder distribution, and the binder is melted by subsequent microwave processing, so that the internal pores of the electrode are further filled, the electrode is further densified, and the distribution of components is more uniform;
4. the invention has simple process and does not need too many mechanical stirring links so as to greatly reduce the material loss; the heating efficiency of the microwave process is high, and the time is short, so that the microwave process is more energy-saving and efficient than the traditional dry process; and the controllability is good in the microwave processing process, so that the repeatability of the sample is good.
Drawings
FIG. 1 is a basic flow chart of the preparation of a solid state electrode by the microwave process of the present invention;
FIG. 2 is a schematic illustration of an active material of the present invention undergoing coating and microwave treatment;
FIG. 3 is a TEM image of an active material coated with a microwaveable material according to example 1 of the invention;
FIG. 4 is SEM images of cross-sections of electrodes treated with and without a microwave process in example 1 and comparative example 1 of the present invention;
fig. 5 is all solid-state battery data for the electrodes prepared in examples 1-2 of the present invention and comparative example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in more detail with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to these embodiments.
A method for preparing a solid state battery electrode by a microwave process:
(1) Coating the wave-absorbing material outside the active substance;
(2) Uniformly mixing the active material with the core-shell structure formed in the step (1) with a conductive agent and an additive to obtain electrode mixed powder;
(3) Pressing the electrode mixed powder obtained in the step (2) into a film;
(4) And (3) putting the film prepared in the step (3) into a special microwave die, and then carrying out microwave processing, wherein a wave-absorbing melting reaction occurs in the electrode, so that a compact electrode is generated.
Example 1
Polyethylene glycol is used as a wave absorbing material, and a spraying process is adopted for coating. 200mg of PEG particles with a molecular weight of 60 ppm are weighed at normal temperature, added with 10ml of deionized water and stirred until the PEG particles are completely dissolved. 700mg LCO,100mg acetylene black are weighed, mixed uniformly, ground for 15min by a mortar and added with an aqueous solution of PEG. After 30min of uniform dispersion, the slurry was added to the spray gun while stirring. Cutting aluminum foil with proper size, tightly adhering to a heating table, vertically placing the heating table, and heating to 250 ℃. And (3) uniformly spraying the slurry on the aluminum foil, taking down the aluminum foil after the spraying is finished, sending the aluminum foil into an oven at 80 ℃ for 3 hours, and scraping and collecting powder on the aluminum foil after the drying is finished. The mass is called 850mg. 90mg of the mixture is placed in a press die, and the pressure is 1.2MPa for 10min. After taking out, the wafer was cut to a size of 12mm in diameter and a thickness of 150. Mu.m. And loading the cut product into a microwave die. The microwave oven was adjusted to 700W power. And (5) carrying out microwave processing for 30S, and taking out to obtain the positive pole piece with the thickness of 120 mu m.
The TEM image of the active material coated with the microwaveable material in this example is shown in fig. 3, and it can be seen from fig. 3 that the active material exhibits a complete coating.
Example 2
Titanium nitride is used as a wave absorbing material, and a vapor deposition process is used for coating. LCO700mg was charged into the reaction chamber. Repeatedly vacuumizing and filling nitrogen, and taking titanium tetrachloride and ammonia as precursors under the protection of the nitrogen, wherein the two gases enter a reaction chamber through independent gas paths. Wherein nitrogen is used as a carrier gas to carry vaporized titanium tetrachloride into the reaction chamber through a bubbler in series. The carrier gas flows of ammonia and titanium tetrachloride were 80 and 150ml/min, respectively, and the nitrogen flow as the shielding gas was 670ml/min, the deposition temperature was 580 ℃, and the deposition time was 360S. And taking out after the deposition is finished, and sending the mixture into an oven at 80 ℃ for 3 hours. And scraping and collecting the powder on the aluminum foil after the drying is finished. The mass is 800mg. 90mg of the mixture is placed in a press die, and the pressure is 5MPa and maintained for 50min. After taking out, the wafer was cut to a size of 12mm in diameter and a thickness of 150. Mu.m. And loading the cut product into a microwave die. The microwave oven was adjusted to 800W power. And (5) carrying out microwave processing for 500S, and taking out to obtain the positive electrode plate with the thickness of 90 mu m.
Comparative example 1
The comparative example provides a conventional lithium ion battery, which is used for preparing a battery anode according to a conventional liquid coating preparation method, and does not comprise the anode plate of the microwave coating process. 700mg of LCO (liquid crystal on silicon) and 100mg of acetylene black are weighed, ground and uniformly mixed, then added into NMP (N-methyl pyrrolidone) solvent of polyvinylidene fluoride (PVDF), continuously ground for 15min, and mapped on an aluminum foil by a coating machine to obtain the anode with the thickness of 100 mu m.
The void ratios of the positive electrodes of the solid-state batteries produced in examples 1, 2 and comparative example 1 are shown in the following table.
Table 1 porosity of different samples
| Sample of | Porosity of the porous material |
| Comparative example | 34％ |
| Example 1 | 3％ |
| Example 2 | 2％ |
Fig. 4 is SEM images of cross sections of the electrodes of example 1 and comparative example 1 treated and not treated by the microwave process; from the figure, the electrodes after microwave treatment were denser.
Example 3
The positive electrode sheets prepared in example 1, example 2 and comparative example 1 were assembled into solid-state batteries, respectively, and solid-state battery assembly tests were performed. The test results are shown in fig. 5, from which it is clear that the electrodes (examples 1 and 2) subjected to the microwave process exhibit better cycle performance.
The above embodiments are merely preferred embodiments of the present invention to illustrate the principles and the effects of the present invention, and are not intended to limit the invention. It should be noted that modifications to the above-described embodiments may be made by one skilled in the art without departing from the spirit and scope of the invention, and such modifications should also be considered as being within the scope of the invention.
Claims (8)
1. A method for preparing a solid state battery electrode by a microwave process, comprising the steps of:
(1) Coating the wave-absorbing material outside the active substance; the wave-absorbing material is a wave-absorbing polymer material, and the wave-absorbing polymer material comprises at least one of polyaniline, polythiophene, polypyrrole, polyethylene glycol, polyamide, polyimide, polyester, polyether, polysulfone and derivatives thereof;
(2) Uniformly mixing the active material with the core-shell structure formed in the step (1) with a conductive agent and an additive to obtain electrode mixed powder;
(3) Pressing the electrode mixed powder obtained in the step (2) into a film;
(4) And (3) filling the film prepared in the step (3) into a die, and then carrying out microwave processing to generate the battery electrode.
2. The method for preparing a solid state battery electrode by a microwave process according to claim 1, wherein the wave-absorbing polymer material is doped with a lithium salt before use, the lithium salt comprising one or more of lithium perchlorate, lithium hexafluoroarsenate, lithium hexafluorophosphate, lithium bisoxalato borate, lithium difluorooxalato borate, lithium bisdifluorosulfonimide and lithium bistrifluoromethylsulfonimide.
3. The method for producing a solid-state battery electrode by a microwave process according to claim 1, wherein the ion conductivity of the wave-absorbing material in the step (1) is 10 -10 -10 -1 S/cm。
4. The method for preparing a solid state battery electrode by a microwave process according to claim 1, wherein the coating method in the step (1) comprises a mechanical mixing method, a solid phase reaction method, a physical and chemical vapor deposition method, a dip coating method, a sol-gel method, a hydrothermal method, a co-precipitation method, an electrodeposition method, a ball milling method, a spray coating method, a microwave method, an electrostatic spray method.
5. The method according to claim 1, wherein the conductive agent in the step (2) is one or more of carbon black, conductive graphite, ketjen black, carbon fiber, carbon nanotube, graphene and mixed conductive agents thereof, and the additive is one or more of a polymer binder, a solid electrolyte and an electrolyte.
6. The method for preparing a solid state battery electrode by a microwave process according to claim 1, wherein the pressing in the step (3) is vacuum hot pressing, atmosphere hot pressing, isostatic pressing, hot isostatic pressing, reaction hot pressing, vibration hot pressing, isostatic pressing, and ultra-high pressure sintering.
7. The method for preparing a solid-state battery electrode according to claim 1, wherein the microwaves in the step (4) are electromagnetic waves with a frequency of 300MHz-300GHz, the waves are in the form of sine waves, cosine waves, square waves, transverse waves and combinations thereof, the microwave power is 10-9000W, and the microwave time is 0.01-3600S.
8. A solid state battery electrode obtained by the method of any one of claims 1-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300487.XA CN114613944B (en) | 2022-03-25 | 2022-03-25 | Method for preparing solid-state battery electrode through microwave process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210300487.XA CN114613944B (en) | 2022-03-25 | 2022-03-25 | Method for preparing solid-state battery electrode through microwave process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114613944A CN114613944A (en) | 2022-06-10 |
| CN114613944B true CN114613944B (en) | 2023-11-21 |
Family
ID=81867030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210300487.XA Active CN114613944B (en) | 2022-03-25 | 2022-03-25 | Method for preparing solid-state battery electrode through microwave process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114613944B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114824280B (en) * | 2022-06-27 | 2022-09-06 | 蚂蚁新能源科技(天津)有限公司 | Composite positive electrode material for lithium ion battery dry-method electrode and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10115928A1 (en) * | 2001-03-30 | 2002-10-10 | Creavis Tech & Innovation Gmbh | Electrolyte membrane, this comprehensive membrane electrode assembly, manufacturing method and special uses |
| CN102664247A (en) * | 2012-04-01 | 2012-09-12 | 上海锦众信息科技有限公司 | Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating |
| CN112186162A (en) * | 2020-09-30 | 2021-01-05 | 西安交通大学 | High-load high-surface-capacity lithium-sulfur battery positive electrode and preparation method and application thereof |
| CN112234249A (en) * | 2020-09-24 | 2021-01-15 | 中国科学院化学研究所 | Composite solid electrolyte, preparation method thereof and application thereof in solid secondary battery |
| CN114122317A (en) * | 2021-11-23 | 2022-03-01 | 蜂巢能源科技(无锡)有限公司 | Positive pole piece for solid-state battery and preparation method and application thereof |
-
2022
- 2022-03-25 CN CN202210300487.XA patent/CN114613944B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10115928A1 (en) * | 2001-03-30 | 2002-10-10 | Creavis Tech & Innovation Gmbh | Electrolyte membrane, this comprehensive membrane electrode assembly, manufacturing method and special uses |
| CN102664247A (en) * | 2012-04-01 | 2012-09-12 | 上海锦众信息科技有限公司 | Method for preparing LiFePO4/SiC lithium battery positive plate by microwave heating |
| CN112234249A (en) * | 2020-09-24 | 2021-01-15 | 中国科学院化学研究所 | Composite solid electrolyte, preparation method thereof and application thereof in solid secondary battery |
| CN112186162A (en) * | 2020-09-30 | 2021-01-05 | 西安交通大学 | High-load high-surface-capacity lithium-sulfur battery positive electrode and preparation method and application thereof |
| CN114122317A (en) * | 2021-11-23 | 2022-03-01 | 蜂巢能源科技(无锡)有限公司 | Positive pole piece for solid-state battery and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114613944A (en) | 2022-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105932225A (en) | Preparation method of improved room temperature electron ion fast transfer electrode slice for solid-state secondary lithium battery | |
| CN112670483B (en) | Positive plate, positive polar plate and solid-state battery | |
| CN113471408B (en) | Method for manufacturing all-solid-state battery composite positive electrode, composite positive electrode and all-solid-state battery | |
| KR20130139804A (en) | Negative electrode meterial for non-aqueous electrolyte secondary battery and manufacturing method thereof | |
| JP6156537B1 (en) | Electrode material for lithium ion secondary battery, electrode for lithium ion secondary battery, and lithium ion secondary battery | |
| US11217826B2 (en) | Methods of making sulfide-impregnated solid-state battery | |
| CN113690406A (en) | Negative electrode and method for producing a negative electrode | |
| CN110350158B (en) | Sulfur composite cathode material and preparation method and application thereof | |
| Chen et al. | PAANa-induced ductile SEI of bare micro-sized FeS enables high sodium-ion storage performance | |
| CN112136233B (en) | Method for producing electrode containing polymer-based solid electrolyte and electrode produced by the method | |
| JP2018163762A (en) | Electrode material for lithium ion secondary battery, method for manufacturing the same, electrode for lithium ion secondary battery and lithium ion secondary battery | |
| KR20200089642A (en) | Negative electrode and secondary battery comprising the negative electrode | |
| CN111162322A (en) | Preparation method of low-temperature lithium ion battery | |
| Lanjapalli et al. | Various advanced permeable substrates for lithium infusion in lithium metal batteries: A review of recent developments | |
| CN114613944B (en) | Method for preparing solid-state battery electrode through microwave process | |
| CN114937770A (en) | Double-layer lithium ion conductor coated modified lithium cobaltate positive electrode material, preparation method thereof, lithium ion battery and electric equipment | |
| EP3940818B1 (en) | Method for producing all-solid-state battery | |
| CN117497723A (en) | Preparation method of MOF-derived carbon-coated silicon nanoparticle-limited MXene composite anode material of lithium ion battery | |
| CN110993953B (en) | Positive plate, solid-state chemical power supply and preparation method | |
| CN110994016A (en) | Polymer solid electrolyte and preparation method and application thereof | |
| JP2017069177A (en) | Electrode material for lithium ion secondary battery, electrode for lithium ion secondary battery and lithium ion secondary battery | |
| CN116404124A (en) | Hard carbon composite material for lithium ion battery and preparation method thereof | |
| Guo et al. | Quasi Solid‐state Electrolytes of Li2Sn2 (bdc) 3 (H2O) x Metal‐organic Frameworks for Lithium Metal Battery | |
| Wang et al. | Preparation of monodispersed ZrO2 nanoparticles and their applications in poly [(vinylidene fluoride)‐co‐hexafluoropropylene]‐based composite polymer electrolytes | |
| Hu et al. | Fabrication of SiO2 nanofiber-integrated all-inorganic electrodes for safer Li-ion batteries |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |