CN114079056B - Heterogeneous cavity structural material and preparation method and application thereof - Google Patents
Heterogeneous cavity structural material and preparation method and application thereof Download PDFInfo
- Publication number
- CN114079056B CN114079056B CN202010837294.9A CN202010837294A CN114079056B CN 114079056 B CN114079056 B CN 114079056B CN 202010837294 A CN202010837294 A CN 202010837294A CN 114079056 B CN114079056 B CN 114079056B
- Authority
- CN
- China
- Prior art keywords
- layer
- shell layer
- heterogeneous
- inner shell
- cavity
- 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
- 239000000463 material Substances 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 62
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 53
- 229910052799 carbon Inorganic materials 0.000 claims description 53
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 43
- 239000003795 chemical substances by application Substances 0.000 claims description 25
- 238000005229 chemical vapour deposition Methods 0.000 claims description 24
- 239000004005 microsphere Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- 229910052582 BN Inorganic materials 0.000 claims description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 14
- 238000000231 atomic layer deposition Methods 0.000 claims description 12
- 150000004767 nitrides Chemical group 0.000 claims description 11
- 238000000151 deposition Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 10
- 239000007772 electrode material Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 8
- 238000005245 sintering Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 238000000197 pyrolysis Methods 0.000 claims description 7
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000011978 dissolution method Methods 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- 239000002052 molecular layer Substances 0.000 claims description 6
- 238000001179 sorption measurement Methods 0.000 claims description 6
- 229920001690 polydopamine Polymers 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- AOPJVJYWEDDOBI-UHFFFAOYSA-N azanylidynephosphane Chemical compound P#N AOPJVJYWEDDOBI-UHFFFAOYSA-N 0.000 claims description 4
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims description 2
- 230000006872 improvement Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 24
- 210000001787 dendrite Anatomy 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 230000005684 electric field Effects 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 161
- 239000000243 solution Substances 0.000 description 33
- 239000002131 composite material Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- 230000005540 biological transmission Effects 0.000 description 11
- 210000004027 cell Anatomy 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 8
- 238000000576 coating method Methods 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000005530 etching Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000000227 grinding Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000000840 electrochemical analysis Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000007704 wet chemistry method Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910017539 Cu-Li Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000003877 atomic layer epitaxy Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000010183 spectrum analysis Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- VXEGSRKPIUDPQT-UHFFFAOYSA-N 4-[4-(4-methoxyphenyl)piperazin-1-yl]aniline Chemical compound C1=CC(OC)=CC=C1N1CCN(C=2C=CC(N)=CC=2)CC1 VXEGSRKPIUDPQT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 238000005234 chemical deposition Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000010326 electrochemical discharging Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011855 lithium-based material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000005049 silicon tetrachloride Substances 0.000 description 1
- 239000011856 silicon-based particle Substances 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The utility model discloses a heterogeneous cavity structure material, which comprises a spherical shell and a cavity formed by the surrounding and the closing of the spherical shell; the spherical shell comprises an outer shell layer and an inner shell layer; the inner shell layer is a conductive layer; the shell layer is a non-conductive layer; the shape of the heterogeneous cavity structural material is a hollow cavity. The heterogeneous cavity structure material has good inner layer conductive performance and poor outer layer closed conductive performance, and when the heterogeneous cavity structure material is applied to a lithium ion battery, the electric field distribution is controlled by different conductivities of different areas of the heterogeneous structure material, so that selective directional deposition of lithium metal is induced, dendrite growth can be effectively inhibited through a thin outer layer to the inside of the cavity, dendrite is isolated from being contacted with electrolyte, the safety performance and the cycle performance of the lithium metal battery are improved, and meanwhile, the preparation method is simple and controllable.
Description
Technical Field
The utility model relates to a heterogeneous cavity structural material, a preparation method and application thereof, and belongs to the technical field of nano materials.
Background
The electrolyte of the lithium ion battery is inflammable, dendrites are easy to form in the electrolyte when the lithium-based material is used as a negative electrode material, and the dendrites grow during charging, so that internal short circuit is easy to cause, and even fire is caused. And lithium metal batteries play a very important role in future high energy density energy storage systems due to their ultra-high specific capacity and lowest redox potential.
Scientific researches show that the design of the cathode material can effectively inhibit dendrite growth. For example, CN209747641U discloses a composite lithium metal negative electrode and a lithium secondary battery, which belongs to the technical field of secondary batteries. The composite lithium metal anode comprises metal lithium and a three-dimensional framework with a cavity; the three-dimensional framework comprises a conductive layer and a layer wrapping the conductive layer, and the layer is tightly attached to the conductive layer; the edge of the three-dimensional framework is of an open pore structure; the metal lithium is filled in the cavity of the three-dimensional framework and is tightly attached to the conductive layer. The composite lithium metal anode can delay the occurrence time of lithium dendrites and control the growth direction of dendrites, so that the growth of the lithium dendrites is inhibited and regulated, and potential safety hazards are eliminated in the electrochemical charging and discharging process; and, because the layer wraps the outside of conducting layer, lithium metal is protected in the operational environment, and lithium metal's stability in the operational environment is improved.
The open structure of the above materials does not solve the side reaction problem caused by dendrite contact with the electrolyte.
Disclosure of Invention
The utility model provides an in-situ grown heterogeneous cavity structure material, which is hollow in the interior and compact in shell layer, and can be used for directional loading and filling of active substances. The heterogeneous cavity structural material has good inner layer conductive performance and poor outer layer closed conductive performance, when the thickness of the inner shell layer is 10-50 nm, the thickness of the outer shell layer is 5-20 nm, and the diameter of the hollow cavity is 50-8000 nm, when the heterogeneous cavity structural material is applied to a lithium ion battery, the selective directional deposition of lithium metal is induced due to different adjustable electric field distribution of the conductivity of the heterogeneous structure, so that the lithium metal passes through an outer thin non-conductive layer to be deposited in a cavity formed by a spherical shell, dendrite growth can be effectively inhibited, dendrite is isolated from being contacted with electrolyte, and the safety performance and the cycle performance of the lithium metal battery are improved.
A heterogeneous cavity structure material, which comprises a spherical shell and a cavity formed by the spherical shell in a surrounding way;
the spherical shell comprises an outer shell layer and an inner shell layer;
the inner shell layer is a conductive layer;
the shell layer is a non-conductive layer;
the shape of the heterogeneous cavity structural material is a hollow cavity.
Optionally, the spherical shell is composed of an outer shell layer and an inner shell layer.
Optionally, the electrical conductivity of the inner shell layer is at least 10S/cm greater than the electrical conductivity of the outer shell layer.
Optionally, the conductive layer is a carbon layer.
Optionally, the non-conductive layer is a nitride layer; the nitride layer is selected from at least one of a phosphorus pentanitride layer, a boron nitride layer, a silicon nitride layer or an aluminum nitride layer.
The conductivity of each material is constant, and the conductivity of the nitride layer of the present utility model is significantly lower than that of the carbon layer.
Optionally, the thickness of the inner shell layer is 5-50 nm, and the thickness of the outer shell layer is 5-20 nm.
Optionally, the diameter of the cavity is 50-8000 nm.
Optionally, the diameter of the cavity is 100-700 nm.
Optionally, the heterogeneous cavity structural material has a hollow cavity shape, and the spherical shell is composed of an outer shell layer and an inner shell layer, wherein the conductivity of the inner shell layer is at least 10S/cm greater than that of the outer shell layer.
Optionally, the electrical conductivity of the inner shell layer is at least 10S/cm greater than the electrical conductivity of the outer shell layer, the thickness of the inner shell layer is 10-50 nm, the thickness of the outer shell layer is 5-20 nm, and the diameter of the cavity is 50-8000 nm.
Optionally, the diameter of the hollow cavity is 200-700 nm.
Optionally, the diameter of the hollow cavity is 80-7000 nm.
In the utility model, the particle size of the prepared template agent such as silicon dioxide microspheres can be adjusted to adjust the diameter of the hollow cavity.
Optionally, the inner shell layer is a conductive layer and the outer shell layer is a non-conductive layer.
Optionally, the inner shell layer is a simple substance layer, and the outer shell layer is a compound layer.
Optionally, the simple substance layer is selected from at least one of a carbon layer, a silicon layer and a boron layer.
Optionally, the compound layer is selected from at least one of an oxide layer, a carbide layer, a nitride layer, a halogen compound layer, and a boride layer.
Optionally, the inner shell layer is a carbon layer, and the outer shell layer is at least one selected from a phosphorus pentanitride layer, a boron nitride layer, a silicon nitride layer, or an aluminum nitride layer.
In the utility model, the thickness of the inner layer and the outer layer can be adjusted by adjusting the dosage of the reactant.
According to a second aspect of the present utility model, a method for preparing the hetero-cavity structure material described above is provided.
The preparation method of the heterogeneous cavity structural material comprises the following steps: and preparing the inner shell layer and the outer shell layer to obtain the heterogeneous cavity structural material.
Optionally, at least comprises:
preparing a template agent;
preparing an inner shell layer by wrapping a template agent;
wrapping the inner shell layer to prepare an outer shell layer;
and removing the template agent to obtain the heterogeneous cavity structure material.
Optionally, the template agent is an inorganic microsphere.
Optionally, the inorganic microspheres are selected from at least one of silica microspheres, alumina microspheres, or iron oxide microspheres.
Optionally, the preparation template agent at least comprises:
synthesizing a template agent by using a precursor source;
the precursor source is selected from at least one of a silicon source, an aluminum source and an iron source.
Optionally, the silicon source is selected from at least one of ethyl orthosilicate, silicon tetrachloride and sodium silicate.
Optionally, the aluminum source is selected from aluminum oxide.
Optionally, the iron source is selected from iron oxide.
Optionally, through improvementSynthesizing the template agent by a method.
Improvement of the designThe method is from the original->The method is developed. Original->The method is a synthesisPhysicochemical method of monodisperse silicon particles by Werner +.>And the like were found first. Generally refers to a method of forming nano silica particles by adding tetraethyl orthosilicate to ethanol and aqueous ammonia. And improved->The method is that a catalyst and a precursor are added into a template solution with charges, and an oxide shell layer is generated on the surface of the template through electrostatic adsorption and hydrolysis.
Optionally, the encapsulating template agent prepares the inner shell layer, comprising at least:
wrapping the mixture containing the raw materials of the inner shell layer on the surface of a template agent, and carbonizing to obtain the inner shell layer;
the inner shell layer is a carbon layer;
and the raw material of the inner shell layer is a carbon source.
Optionally, the carbon source is selected from at least one of sucrose, glucose, fructosyl, polydopamine, methane, acetylene, or carbon.
Optionally, the method for preparing the inner shell layer by wrapping the template agent is at least one selected from a chemical vapor deposition method, a hydrothermal method and a chemical adsorption method.
Specifically, the choice of the type of carbon source is determined by the method of preparing the inner shell layer by encapsulating the templating agent. If a hydrothermal method is selected, the carbon source can be selected from sucrose, glucose, fructosyl poly (dopamine), and the like; when chemical vapor deposition is used, the carbon source may be methane.
Chemical Vapor Deposition (CVD) is mainly to produce a thin film by chemical reaction of one or more vapor compounds or elements containing thin film elements on the surface of a substrate. Chemical vapor deposition is a new technology developed over the last decades to produce inorganic materials. Chemical vapor deposition has been widely used to purify materials, develop new crystals, deposit various single crystal, polycrystalline or glassy inorganic thin film materials.
The hydrothermal process is to use water solution as reaction medium in a specially made sealed reaction container (high pressure reaction kettle) and to heat the reaction container to create one high temperature (100-1000 deg.c) and high pressure (1-100 MPa) reaction environment for dissolving and re-crystallizing insoluble matter. Hydrothermal processes have been widely used for material preparation, chemical reactions and treatments and are a very active area of research. It is defined as: hydrothermal processes refer to the general term for chemical reactions carried out in fluids such as water, aqueous solutions or vapors at elevated temperature and pressure.
Optionally, the carbonization conditions are: sintering for 2-6 h at 800-1000 ℃ in the inert gas atmosphere.
Preferably, the carbonization conditions are: and sintering for 2 hours at 800 ℃ in an inactive gas atmosphere.
Preferably, the carbonization conditions are: sintering for 2h at 1000 ℃ in an inactive gas atmosphere.
In the utility model, the sintering temperature exceeds 1000 ℃, and the carbon spheres are damaged in the sintering process.
Optionally, the inactive gas is selected from at least one of argon and nitrogen.
Optionally, the outer shell layer is prepared by wrapping the inner shell layer, and at least comprises:
wrapping the mixture containing the shell layer raw material on the surface of an inner shell layer to obtain the shell layer;
the shell layer is a nitride layer;
the shell layer is made of nitride.
Optionally, the nitride is selected from at least one of phosphorus pentanitride, boron nitride, silicon nitride, or aluminum nitride.
Optionally, the method for preparing the outer shell layer by wrapping the inner shell layer is at least one selected from a chemical vapor deposition method, an atomic layer deposition method and a molecular layer deposition method.
Atomic layer deposition is a process by which substances can be plated onto a substrate surface layer by layer in the form of monoatomic films. Atomic layer deposition is similar to common chemical deposition. However, during atomic layer deposition, the chemical reaction of a new atomic layer is directly related to the previous layer in such a way that only one atomic layer is deposited per reaction. Monoatomic layer deposition (atomic layer deposition, ALD), also known as atomic layer deposition or atomic layer epitaxy (atomic layer epitaxy)
Optionally, the method for removing the template agent is at least one selected from a pyrolysis method, a wet chemical method and a solvent dissolution method.
Specifically, in the embodiments of the present utility model, pyrolysis refers to sintering at high temperature to oxidize and remove the template layer in air; wet chemistry refers to the removal of at least a portion of the template layer using a liquid compound reaction, and solvent dissolution refers to the removal of at least a portion of the template layer using solvent dissolution.
In an alternative embodiment, the templating agent is an inorganic oxide microsphere, such as a silica microsphere, and the removing the template layer comprises:
the inorganic oxide microspheres are reacted off by wet chemistry.
In another alternative embodiment, the templating agent is an inorganic metal oxide, such as iron oxide microspheres, and the removing the template layer comprises:
the inorganic metal oxide microspheres are removed by wet chemistry.
In a specific embodiment, the preparation method of the heterogeneous cavity structure material includes:
adopts improvementSynthesizing by a method or directly purchasing and preparing a template phase; adopting a Chemical Vapor Deposition (CVD) technology, a hydrothermal method and a chemical adsorption method to prepare a conductive layer; preparing a non-conductive layer by adopting a chemical vapor deposition method, atomic layer deposition and molecular layer deposition; and removing the template phase material of the composite material by adopting a wet chemical method, a high-temperature pyrolysis method and a solvent dissolution method.
Specifically, the preparation method of the heterogeneous cavity structure material provided by the embodiment comprises the following steps:
step S100: adopts improvementSynthesizing by a method or directly purchasing to prepare a nano template phase;
step S200: adopting a Chemical Vapor Deposition (CVD) technology, a hydrothermal method and a chemical adsorption method to prepare a conductive layer;
step S300: preparing a non-conductive layer by adopting a chemical vapor deposition method, atomic layer deposition and molecular layer deposition;
step S400: and removing the template phase material of the composite material by adopting a wet chemical method, a pyrolysis method and a solvent dissolution method to obtain the heterogeneous cavity composite material, which is applied to the protection of lithium metal batteries.
According to a third aspect of the present utility model, there is provided an electrode material.
An electrode material comprises at least one of the heterogeneous cavity structure material and the heterogeneous cavity structure material prepared by the preparation method.
According to a fourth aspect of the present utility model, a lithium ion battery is provided.
A lithium ion battery, the negative electrode of which comprises the electrode material.
Optionally, the negative electrode is the electrode material described above.
The utility model is improvedThe method comprises a hydrothermal method, a chemical adsorption method, a chemical vapor deposition method, an atomic layer deposition method, a molecular layer deposition method, a wet chemical method, a pyrolysis method and a solvent dissolution method. The diameter and the layer thickness of the cavity are adjustable. Meanwhile, the electric field distribution is regulated and controlled by the conductivity difference of the heterogeneous cavity structure, and lithium metal can be directionally deposited into the cavity. The method has the advantages of simple process, low cost and easy operation.
The method is adopted to controllably adjust the particle size of the template and the surface charge of the template by adjusting the template synthesis conditions and the deposition conditions, such as the types of the initiator, the amount of raw materials, the reaction time, the reaction temperature, the molecular weight of the dispersing agent, the deposition time, the gas flow and the like. The method is simple and controllable, and is environment-friendly.
The utility model has the beneficial effects that:
(1) The heterogeneous cavity structural material provided by the utility model can adjust the particle size of the material and the thickness of a deposited shell layer according to the needs, is favorable for loading and filling active substances, and meets different application requirements.
(2) The preparation method of the heterogeneous cavity structure material provided by the utility model is improvedPreparing a heterogeneous layer structure composite material by one or more of a method, a chemical vapor deposition method, atomic layer deposition and molecular layer deposition; and removing the template phase material of the composite material by adopting a wet chemical method, a pyrolysis method and a solvent dissolution method to form a cavity structure compounded by materials with different conductivities. The preparation method has simple process, and the used equipment is industrialized experimental equipment, so that the preparation method has good application prospect. The method has the advantages of simple process, low cost and easy operation, and can prepare the impurity-free compact nano-scale or micro-scale heterogeneous cavity structure material.
(3) According to the heterogeneous cavity structural material provided by the utility model, the specific electric fields are regulated and controlled by different conductivities of the heterogeneous materials, and the whole structure is compact and sealed, so that lithium can be deposited into the cavity through the thin non-conductive outer layer. The utility model is applied to the lithium metal cathode protection, can effectively inhibit dendrite growth and volume change, isolate lithium metal from contacting electrolyte, inhibit side reaction and improve the safety performance and the cycling stability of the lithium metal battery.
Drawings
FIG. 1 is an SEM image of silica microspheres of heterogeneous cavity structure material 1# intermediate prepared in example 1 of the present utility model;
FIG. 2 is a TEM image of a heterogeneous cavity structure material 5# intermediate carbon coated silica composite sphere prepared in example 5 of the present utility model;
FIG. 3 is a TEM image of a heterogeneous cavity structure material 1# intermediate carbon-coated silica composite sphere prepared in example 1 of the present utility model;
FIG. 4 is an SEM image of broken hollow carbon spheres of the intermediate product of the hetero-cavity structure material D1# prepared in comparative example 1 of the present utility model;
FIG. 5 is a TEM image of a heterogeneous cavity structure material 2# intermediate carbon coated silica composite sphere prepared in example 2 of the present utility model;
FIG. 6 is an SEM image of a heterogeneous cavity structure material 3# intermediate carbon coated silica composite sphere prepared in example 3 of the present utility model;
FIG. 7 is an SEM image of a heterogeneous cavity structure material 2# intermediate carbon coated silica composite sphere prepared in example 2 of the present utility model;
FIG. 8 is a transmission electron microscope (TEM, 20 nm) image of the hetero-cavity structure material 1# prepared in example 1 of the present utility model;
FIG. 9 is a high resolution transmission plot (TEM, 5 nm) of heterogeneous cavity structure material 1# prepared in example 1 of the present utility model;
FIG. 10 is a C, B, N energy spectrum analysis of a high-resolution transmission diagram of a hetero-cavity structure material 1# prepared in example 1 of the present utility model;
fig. 11 is a graph showing electrochemical test performance of 2032 button cell made of heterogeneous cavity structure material 1# prepared in example 1 of the present utility model, and cycling stability from half cell to 145 cycles.
Fig. 12 is charge and discharge curves of circles 1 and 90 of 2032 button cell made of heterogeneous cavity structure material 1# prepared in example 1 of the present utility model.
Fig. 13 is an electrochemical test performance graph of 2032 button cell made of heterogeneous cavity structure material d1# prepared in comparative example 1.
Fig. 14 is an electrochemical test performance graph of a conventional Cu-Li battery.
Detailed Description
The present utility model is described in detail below with reference to examples, but the present utility model is not limited to these examples.
Unless otherwise indicated, all starting materials in the examples of the present utility model were purchased commercially. If not specified, the test methods are all conventional methods, and the instrument settings are all recommended by manufacturers.
The morphological characteristics of the samples were analyzed by Scanning Electron Microscope (SEM) testing, the analytical instrument was a field emission scanning electron microscope thermal field Sirion200, and the test conditions were a voltage of 5kV.
The internal structural characteristics and element composition information of the sample are analyzed by a Transmission Electron Microscope (TEM) test, the analysis instrument is a transmission electron microscope Tecnai F20, and the test condition is a voltage of 200kV.
Example 1 preparation of heterogeneous Cavity Structure Material 1#
Improved stoner method for preparing silicon dioxide microsphere
Preparing a1 solution comprising 32.5mL C 2 H 5 OH，49.5mL H 2 O,9mL ammonia (25 wt%), rapidly stirred for 11 minutes;
preparing solution b1 including 91mL C 2 H 5 OH,6.75mL tetraethyl silicate (TEOs, 28.4 wt%) solution, rapidly stirred for 10 minutes;
the b1 solution was added to the a1 solution rapidly, and after stirring rapidly for 5min, stirring was carried out at 600rpm for 6h.
Washing the reacted solution with water, washing with alcohol for three times, filtering, and dispersing in ethanol for standby.
Coating carbon by a hydrothermal method:
preparing solution a, including 4g glucose, 0.25g polyvinylpyrrolidone (PVP), 15mL H 2 O, rapidly stirring until the solution is transparent;
preparing a solution b comprising 0.4g of the above SiO 2 Microspheres, 0.25g polyvinylpyrrolidone (PVP), 15mL H 2 O, performing ultrasonic dispersion for 1h;
and (3) rapidly adding the solution b into the solution a, stirring for 10min, and then placing into a reaction kettle for reaction at 160 ℃ for 16h.
After the reaction, the mixture is washed with water and dried.
The solid prepared above was ground into powder, placed in a tube furnace, continuously purged with argon at a rate of 150sccm (sccm means Standard Cubic Centimeter per Minute, standard ml/min), and sintered for 2 hours at a temperature rising rate of 5 ℃/min to 800 ℃.
CVD method for coating boron nitride
Grinding the prepared solid into powder, putting the powder into a tube furnace, continuously introducing argon at a rate of 150sccm, simultaneously placing a crucible containing 2g boric acid above the air flow, heating to 800 ℃ at a heating rate of 5 ℃/min, introducing ammonia for 2h, stopping introducing ammonia, and simultaneously cooling.
Etching a template:
the solid powder prepared above was put into 2mL of concentrated hydrofluoric acid (40 wt%) solution, and after 12 hours of etching, diluted with water, filtered and dried. And forming a heterogeneous cavity structure material 1# with the inner layer being a carbon layer and the outer layer being a boron nitride layer.
Using a scanning electron microscope and a transmission electron microscope for characterization, wherein the heterogeneous cavity structural material 1# is a hollow cavity structure, fig. 1 is an SEM image of a silica microsphere of a heterogeneous cavity structural material 1# intermediate product, the diameter of the silica microsphere is 200nm, the diameter of a hollow cavity of a sample 1# is deduced to be 200nm, fig. 3 is a TEM image of a carbon-coated silica composite sphere of the heterogeneous cavity structural material 1# intermediate product, according to the contrast, the inside of the material is solid, the outer diameter is 220nm, the outer layer low-contrast part is a carbon layer, and the thickness is uniform and is 20nm; fig. 8 is a transmission electron microscope (TEM, 20 nm) of the hetero-cavity structure material 1#, fig. 9 is a high-resolution transmission diagram (TEM, 5 nm) of the hetero-cavity structure material 1#, two layers of different materials can be seen from the contrast, fig. 10 is a C, B, N energy spectrum analysis of the high-resolution transmission diagram of the hetero-cavity structure material 1#, it can be seen that the carbon layers are uniformly distributed, B, N elements are mainly distributed in the outer shell layer, and the composition of the hetero-cavity structure can be obtained in combination with fig. 9: the outermost layer is BN layer, the inner layer is carbon layer, and the middle is hollow cavity. In conclusion, the diameter of the hollow cavity of the heterogeneous cavity structural material 1# is 200nm, the thickness of the carbon layer is 15nm, and the thickness of the boron nitride layer is 5nm.
Example 2 preparation of heterogeneous Cavity Structure Material 2#
Improved stoner method for preparing silicon dioxide microsphere
Preparing a1 solution comprising 32.5mL C 2 H 5 OH，49.5mL H 2 O,9mL ammonia (25 wt%), rapidly stirred for 11 minutes;
preparing solution b1 including 91mL C 2 H 5 OH,6.75mL tetraethyl silicate (TEOs, 28.4 wt%) solution, rapidly stirred for 10 minutes;
the b1 solution was added to the a1 solution rapidly, and after stirring rapidly for 5min, stirring was carried out at 600rpm for 6h.
Washing the reacted solution with water, washing with alcohol for three times, filtering, and dispersing in ethanol for standby.
Poly-dopamine to carbon:
10mM Tris solution was prepared, adjusted to pH=8.5 by adding 1M HCl solution, and 0.3g SiO was added 2 Adding the microspheres into the solution, performing ultrasonic treatment for 2 hours, adding 0.3g of polydopamine (DA), stirring at room temperature for 6 hours, washing with alcohol and water for three times after the reaction is finished, and performing vacuum drying.
Grinding the prepared solid into powder, putting the powder into a tube furnace, continuously introducing argon at a rate of 150sccm, heating to 800 ℃ at a heating rate of 5 ℃/min, and sintering for 2 hours for carbonization.
CVD method for coating boron nitride
Grinding the prepared solid into powder, putting the powder into a tube furnace, continuously introducing argon at a rate of 150sccm, simultaneously placing a crucible containing 2g boric acid above the air flow, heating to 800 ℃ at a heating rate of 5 ℃/min, introducing ammonia for 2h, stopping introducing ammonia, and simultaneously cooling.
Etching a template:
the prepared solid powder is put into 2mL of concentrated hydrofluoric acid solution, and is diluted by water, filtered and dried after 12h of etching. And forming a heterogeneous cavity structural material No. 2, wherein the inner layer is a carbon layer and the outer layer is a boron nitride layer.
Using a scanning electron microscope and a transmission electron microscope for characterization, fig. 5 is a TEM image of a heterogeneous cavity structural material 2# intermediate product carbon coated silica composite sphere, and according to the contrast, it can be seen that the material is solid inside and has an outer diameter of 210nm, wherein the outer layer low contrast part is a carbon layer, and the shell layer is about 10nm; fig. 7 is an SEM image of heterogeneous cavity structure material 2# intermediate carbon coated silica composite spheres, the overall microsphere CVD carbon coated is uniform, and the circled portion is the excess carbon of the silica surface CVD. In conclusion, the heterogeneous cavity structural material No. 2 is of a hollow cavity structure, the diameter of the hollow cavity is 200nm, the thickness of the carbon layer is 8nm, and the thickness of the boron nitride layer is 5nm.
Example 3 preparation of heterogeneous Cavity Structure Material 3#
Improved stoner method for preparing silicon dioxide microsphere
Preparing a1 solution comprising 32.5mL C 2 H 5 OH，49.5mL H 2 O,9mL of ammonia water, and rapidly stirring for 11 minutes;
preparing solution b1 including 91mL C 2 H 5 OH,6.75mL tetraethyl silicate (TEOs, 28.4 wt%) solution, rapidly stirred for 10 minutes;
the b1 solution was added to the a1 solution rapidly, and after stirring rapidly for 5min, stirring was carried out at 600rpm for 6h.
Washing the reacted solution with water, washing with alcohol for three times, filtering, and dispersing in ethanol for standby.
CVD carbon coating:
0.3g of SiO 2 Placing the powder into a tube furnace, introducing 150sccm argon and 10sccm hydrogen, heating to 1100deg.C at 5deg.C/min, maintaining for 20min, introducing 5sccm methane, maintaining for 20min, stopping introducing methane, stopping heating, and naturally cooling.
CVD method for coating boron nitride
Grinding the prepared solid into powder, putting the powder into a tube furnace, continuously introducing argon at a rate of 150sccm, simultaneously placing a crucible containing 2g boric acid above the air flow, heating to 800 ℃ at a heating rate of 5 ℃/min, introducing ammonia for 2h, stopping introducing ammonia, and simultaneously cooling.
Etching a template:
the prepared solid powder is put into 2mL of concentrated hydrofluoric acid solution, and is diluted by water, filtered and dried after 12h of etching. And forming a heterogeneous cavity structure material 3# with the inner layer being a carbon layer and the outer layer being a boron nitride layer.
Using scanning electron microscopy, transmission electron microscopy for characterization, fig. 6 is an SEM image of a heterogeneous cavity structural material 3# intermediate carbon coated silica composite sphere, compared with fig. 1, the outer layer of fig. 6 is rough and obvious, illustrating that carbon has been wrapped in the outer layer, wherein the circled portion is redundant carbon of the silica surface CVD; the heterogeneous cavity structural material 3# is a hollow cavity structure, the diameter of the hollow cavity is 200nm, the thickness of the carbon layer is 5nm, and the thickness of the boron nitride layer is 5nm.
Example 4 preparation of heterogeneous Cavity Structure Material 4#
The procedure is as in example 1, except that the template is changed and the hydrothermal glucose is used to carbonize using a commercially available alumina powder (0.20 μm).
Etching a template: the solid powder prepared above was put into 5mL of concentrated hydrochloric acid (36.5 wt%) solution, reacted for 12 hours, neutralized with 40mL of dilute sodium hydroxide solution (10 wt%), washed with deionized water, and centrifugally dried. And obtaining a heterogeneous cavity structural material No. 4, wherein the inner layer is a carbon layer, and the outer layer is a boron nitride layer.
And a scanning electron microscope and a transmission electron microscope are used for characterization, wherein the heterogeneous cavity structural material 4# is a hollow cavity structure, the diameter of the hollow cavity is 200nm, the thickness of the carbon layer is 15nm, and the thickness of the boron nitride layer is 5nm.
Example 5 preparation of heterogeneous Cavity Structure Material 5#
The preparation method is basically the same as that of example 1, except that the glucose addition amount is 2g, the obtained heterogeneous cavity structural material 5# is characterized in that the inner layer is a carbon layer, the outer layer is a boron nitride layer, the appearance is a hollow cavity, the diameter of the hollow cavity is 200nm, the thickness of the carbon layer is 5nm, and the thickness of the boron nitride layer is 5nm. Fig. 2 is a TEM image of a heterogeneous cavity structure material 5# intermediate carbon coated silica composite sphere, and according to the contrast, it can be seen that the material is solid inside and has an outer diameter of 210nm, and the outer layer low-contrast portion is a carbon layer and is not uniform enough.
Comparative example 1
The preparation method is basically the same as that of example 1, except that the carbonization temperature is 1100 ℃, and the obtained hetero-cavity structural material D1# is a damaged hollow carbon sphere, the inner diameter is 190nm, and the thickness of the carbon layer is 20nm. Fig. 4 is an SEM image of hollow carbon spheres broken by intermediate product of heterogeneous cavity structure material d1# at too high a temperature and broken shell.
Example 6 preparation of hetero-Cavity Structure Material electrode
The heterogeneous cavity structural materials obtained in examples 1 to 5 and comparative example 1 were respectively used as active materials, mixed with a binder polyvinylidene fluoride PVDF in a mass ratio of 9:1, and stirred at room temperature for 8 hours with N-methylpyrrolidone NMP as a mixed solvent to obtain a mixed slurry. And (3) coating the mixed slurry on the surface of a copper mesh by adopting a coating machine by a coating method, vacuum drying at 120 ℃ for 24 hours to obtain electrode materials 1-5 and 1', and respectively cutting the electrode materials 1-5 and 1' into pole pieces with the diameter of 16mm to obtain electrodes 1-5 (respectively corresponding to examples 1-5) and electrode 1' (corresponding to comparative example 1).
Example 7 preparation of lithium ion Battery
The half-cells 1 to 5 and the half-cell 1 'are prepared by adopting the electrodes 1 to 5 and the electrode 1', respectively.
The specific battery mounting steps are as follows:
firstly, respectively taking electrodes 1 to 5 and electrode 1' as working electrodes, and taking a lithium sheet as a counter electrode, wherein the component of electrolyte is V (EC); (DEC) =1:1 as solvent, 1M LiPF6 as solute. The above materials were then assembled 2032 into coin cells 1-5, 1' in a glove box.
Example 8 electrochemical Performance test of lithium batteries
The 2032 button cells 1 to 5, 1' and the conventional cu—li battery made in example 7 were subjected to cycle performance test in the following steps:
at 0.5mA/cm 2 The charge and discharge were performed under the test conditions of 2 hours. The test was performed after 1, 2, 10, 50, 100, 150, 200 cycles with charge-discharge as one cycle, referred to as 1 cycle. Representative of 2032 button cell 1 (made from heterogeneous cavity structure material 1# material from example 1) is a cycling schematic of electrochemical performance as shown in fig. 11. When the heterogeneous cavity structure 1# is used as an electrode material, the coulomb efficiency of the battery can reach more than 98% until after 145 circles are circulated, no obvious change exists, and the material shows good electrochemical stability. 2032 coin cells 2-5 the test results were consistent with 2032 coin cell 1. Whereas 2032 button cell 1' had only 50 cycles, the conventional Cu-Li cell had less than 50 cycles.
While the utility model has been described in terms of preferred embodiments, it will be understood by those skilled in the art that various changes and modifications can be made without departing from the scope of the utility model, and it is intended that the utility model is not limited to the specific embodiments disclosed.
Claims (6)
1. The heterogeneous cavity structure material is characterized by comprising a spherical shell and a cavity formed by the spherical shell in a surrounding manner;
the spherical shell comprises an outer shell layer and an inner shell layer;
the inner shell layer is a conductive layer, and the conductive layer is a carbon layer;
the shell layer is a non-conductive layer, and the non-conductive layer is a nitride layer;
the nitride layer is at least one selected from a phosphorus pentanitride layer, a boron nitride layer, a silicon nitride layer or an aluminum nitride layer;
the shape of the heterogeneous cavity structural material is a hollow cavity;
the thickness of the inner shell layer is 5-50 nm, and the thickness of the outer shell layer is 5-20 nm;
the diameter of the cavity is 100-700 nm;
the electrical conductivity of the inner shell layer is at least 10S/cm greater than the electrical conductivity of the outer shell layer;
the preparation method of the heterogeneous cavity structure material at least comprises the following steps:
preparing a template agent: the template agent is at least one of silicon dioxide microspheres, aluminum oxide microspheres or ferric oxide microspheres;
preparing an inner shell layer by wrapping a template agent: wrapping the mixture containing the raw materials of the inner shell layer on the surface of a template agent, and carbonizing to obtain the inner shell layer; the inner shell layer is a carbon layer; the inner shell layer raw material is a carbon source;
the method for preparing the inner shell layer by wrapping the template agent is at least one of a chemical vapor deposition method, a hydrothermal method and a chemical adsorption method;
preparation of the outer shell layer by wrapping the inner shell layer: wrapping the mixture containing the shell layer raw material on the surface of an inner shell layer to obtain the shell layer; the shell layer is a nitride layer; the shell layer raw material is nitride;
the method for preparing the outer shell layer by wrapping the inner shell layer is at least one of a chemical vapor deposition method, an atomic layer deposition method and a molecular layer deposition method;
removing the template agent: the method for removing the template agent is at least one selected from a pyrolysis method, a wet chemical method and a solvent dissolution method, so that the heterogeneous cavity structural material is obtained.
2. The heterogeneous cavity structural material of claim 1, wherein the preparation of the templating agent comprises at least:
synthesizing a template agent by using a precursor source;
the precursor source is selected from at least one of a silicon source, an aluminum source and an iron source;
by improvement ofSynthesizing the template agent by a method.
3. The heterogeneous cavity structural material of claim 1, wherein the carbon source is selected from at least one of sucrose, glucose, fructosyl, polydopamine, methane, acetylene, or carbon.
4. The heterogeneous cavity structural material of claim 1, wherein the carbonization conditions are: sintering for 2-6 h at 800-1000 ℃ in the inert gas atmosphere.
5. An electrode material comprising at least one of the hetero-cavity structure materials according to any one of claims 1 to 4.
6. A lithium ion battery, wherein the negative electrode is the electrode material of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010837294.9A CN114079056B (en) | 2020-08-19 | 2020-08-19 | Heterogeneous cavity structural material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010837294.9A CN114079056B (en) | 2020-08-19 | 2020-08-19 | Heterogeneous cavity structural material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114079056A CN114079056A (en) | 2022-02-22 |
| CN114079056B true CN114079056B (en) | 2023-10-31 |
Family
ID=80282260
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010837294.9A Active CN114079056B (en) | 2020-08-19 | 2020-08-19 | Heterogeneous cavity structural material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114079056B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2996801A1 (en) * | 2015-09-03 | 2017-06-01 | Navitas Systems, Llc | Metal nitride or oxinitride material for lithium sulfur batteries |
| CN108232167A (en) * | 2018-01-19 | 2018-06-29 | 洛阳理工学院 | A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof |
| CN113224273A (en) * | 2020-02-05 | 2021-08-06 | 中国科学院宁波材料技术与工程研究所 | Heterogeneous cavity structure material and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160015652A1 (en) * | 2012-02-16 | 2016-01-21 | The Administrators Of The Tulane Educational Fund | Hollow nanoparticles with hybrid double layers |
-
2020
- 2020-08-19 CN CN202010837294.9A patent/CN114079056B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2996801A1 (en) * | 2015-09-03 | 2017-06-01 | Navitas Systems, Llc | Metal nitride or oxinitride material for lithium sulfur batteries |
| CN108232167A (en) * | 2018-01-19 | 2018-06-29 | 洛阳理工学院 | A kind of carbon@ferrosilites hollow-core construction compound and preparation method thereof |
| CN113224273A (en) * | 2020-02-05 | 2021-08-06 | 中国科学院宁波材料技术与工程研究所 | Heterogeneous cavity structure material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114079056A (en) | 2022-02-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111180691B (en) | Double-layer carbon-coated silicon-based composite material and preparation method and application thereof | |
| US10333141B2 (en) | Silicon-silicon oxide-lithium composite material having nano silicon particles embedded in a silicon:silicon lithium silicate composite matrix, and a process for manufacture thereof | |
| CN111180693B (en) | Negative active material, preparation method and application thereof | |
| Wang et al. | Controllable synthesis of SnO 2@ C yolk–shell nanospheres as a high-performance anode material for lithium ion batteries | |
| WO2019161288A1 (en) | Silicon-carbon nanomaterials, method of making same, and uses of same | |
| JP2019533878A (en) | Silicon: Volume change compensated silicon-silicon oxide-lithium composite with silicon nanoparticles embedded in silicon lithium silicate composite substrate, and iterative off-site manufacturing process | |
| WO2013017101A2 (en) | Mesoporous silicon composite used as cathode material for lithium-ion batteries and preparation method therefor | |
| Jeong et al. | High-performance characteristics of silicon inverse opal synthesized by the simple magnesium reduction as anodes for lithium-ion batteries | |
| WO2023241148A1 (en) | Negative electrode material, and negative electrode sheet and battery comprising same | |
| JP6822500B2 (en) | Conductive material for lithium ion secondary battery, composition for forming negative electrode of lithium ion secondary battery, composition for forming positive electrode of lithium ion secondary battery, negative electrode for lithium ion secondary battery, positive electrode for lithium ion secondary battery and lithium ion secondary Next battery | |
| CN111463419B (en) | Silicon-based @ titanium niobium oxide core-shell structure anode material and preparation method thereof | |
| CN113506861B (en) | Silicon-based composite negative electrode material of lithium ion battery and preparation method thereof | |
| CN109888256B (en) | Si @ SiOx@ nitrogen doped TiO2-δMaterial, preparation method and application thereof | |
| CN105705460A (en) | Method for preparing hollow silicon spheres as well as hollow silicon spheres prepared therefrom | |
| CN108682833B (en) | Preparation method of lithium iron phosphate-based modified cathode material | |
| JP7455425B2 (en) | Silicon/silicon oxide-carbon composite material, its preparation method, and negative electrode active material for lithium secondary batteries containing the same | |
| WO2023125171A1 (en) | Negative electrode material and preparation method therefor, and lithium-ion battery | |
| CN112219295B (en) | Silicon-based lithium storage material and preparation method thereof | |
| WO2023208058A1 (en) | Negative electrode sheet, preparation method therefor, battery, and preparation method for negative electrode material | |
| Yoon et al. | High-conversion reduction synthesis of porous silicon for advanced lithium battery anodes | |
| Yao et al. | Multilayer Si@ SiOx@ void@ C anode materials synthesized via simultaneously carbonization and redox for Li-ion batteries | |
| Sun et al. | Comparative study of electrochemical performance of SnO2 anodes with different nanostructures for lithium-ion batteries | |
| CN112467097A (en) | Negative electrode material, preparation method thereof, electrode and secondary battery | |
| CN114079056B (en) | Heterogeneous cavity structural material and preparation method and application thereof | |
| CN114361414B (en) | Composite material, preparation method thereof and battery |
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 |