CN109841897B - Preparation method of all-solid-state fluorine ion battery based on atomic layer deposition - Google Patents
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 42
- 238000000231 atomic layer deposition Methods 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 235000012431 wafers Nutrition 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 8
- 239000013543 active substance Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 55
- 239000010408 film Substances 0.000 claims description 55
- 239000002243 precursor Substances 0.000 claims description 48
- 238000000151 deposition Methods 0.000 claims description 37
- 230000008021 deposition Effects 0.000 claims description 28
- 238000004140 cleaning Methods 0.000 claims description 24
- 239000002994 raw material Substances 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 claims description 3
- 229910021620 Indium(III) fluoride Inorganic materials 0.000 claims description 3
- 229910002319 LaF3 Inorganic materials 0.000 claims description 3
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 3
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910001637 strontium fluoride Inorganic materials 0.000 claims description 3
- FVRNDBHWWSPNOM-UHFFFAOYSA-L strontium fluoride Chemical compound [F-].[F-].[Sr+2] FVRNDBHWWSPNOM-UHFFFAOYSA-L 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- JNLSTWIBJFIVHZ-UHFFFAOYSA-K trifluoroindigane Chemical compound F[In](F)F JNLSTWIBJFIVHZ-UHFFFAOYSA-K 0.000 claims description 3
- 230000014759 maintenance of location Effects 0.000 abstract description 5
- 238000007599 discharging Methods 0.000 abstract description 2
- 229910010342 TiF4 Inorganic materials 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000004044 response Effects 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- -1 fluoride anions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of an all-solid-state fluorine ion battery based on atomic layer deposition, which takes glass or silicon wafers as substrates, adopts the atomic layer deposition method to sequentially deposit metal films as a positive current collector, a deposited metal fluoride film as a positive active substance, a deposited fluoride film as a solid electrolyte, and a deposited metal film as a negative and negative current collector films, and finishes the preparation of the all-solid-state fluorine ion battery. The ionic conductivity of the all-solid-state fluorine ion battery prepared by the method can reach 10‑5～10‑4S/cm; after 100 times of charging and discharging, the capacity retention rate is still more than 95%.
Description
Technical Field
The invention belongs to the technical field of electric energy materials, and particularly relates to a preparation method of an all-solid-state fluorine ion battery based on atomic layer deposition.
Background
Currently, the commercial secondary battery is mainly based on the lithium ion battery technology. A lithium ion battery is a secondary battery that is composed of a positive electrode material and a negative electrode material using a lithium storage compound, and lithium ions (Li +) are exchanged between the positive electrode and the negative electrode when the battery is cycled. With the recent continuous development of lithium ion battery technology and the continuous development of new materials, lithium ion batteries have been widely used in the fields of portable electronic devices, electric vehicles, aerospace, and the like. However, the performance indexes such as energy density, cycle life, and environmental compatibility have not been able to be fully satisfied in response to the increasing demands of rapid development in the above fields. Particularly, the capability of rapid charge and discharge and the potential safety hazard caused by the decomposition of the electrolyte become two more prominent controversial hotspots. In addition, lithium availability is also a concern for large scale applications. Researchers are actively exploring new alternative technologies while constantly improving lithium ion battery technologies. Many new designs have been developed for anion-based fluoride ion batteries and cation-based sodium, magnesium, and aluminum-based batteries. Among these, fluorine ion batteries are particularly spotlighted due to their high energy density and their great improvement in safety.
A fluoride ion battery is a secondary battery comprising a fluoride-containing electrolyte, a metal anode and a metal fluoride cathode, and containing no lithium or lithium ions, and fluoride anions (F) when the battery is cycled-) Exchange between the positive and negative electrodes, and act as ion transport media. Fluorine anions have a very large change in free energy during the conversion between the two poles, and therefore fluorine ion batteries have a very high theoretical potential. Meanwhile, when the cathode material is binary or ternary metal fluoride, each metal atom can obtain a plurality of electrons through reaction, so that the fluorine ion battery has higher energy density. Studies have shown that the theoretical energy density of fluoride ion batteries can be as high as 5000Wh/L, about 50% higher than that of lithium air batteries. In addition, the fluorine ion battery may use a solid crystal as its electrolyte material. The all-solid-state composition form can effectively avoid potential safety hazards caused by decomposition and leakage of electrolyte in the conventional lithium ion battery.
Disclosure of Invention
The invention provides a preparation method of an all-solid-state fluorine ion battery, which can effectively improve the compactness of a prepared solid electrolyte and improve the contact effect of an electrode/electrolyte interface; thereby effectively reducing the impedance of the all-solid-state thin-film fluorine ion battery and improving the performance of the all-solid-state fluorine ion battery; meanwhile, the preparation method is simple to operate and easy to popularize.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of an all-solid-state fluorine ion battery based on atomic layer deposition is characterized in that glass or silicon wafers are used as substrates, metal films are sequentially deposited by adopting the atomic layer deposition method to serve as a positive current collector, a metal fluoride film is deposited to serve as a positive active substance, a fluoride film is deposited to serve as a solid electrolyte, and a metal film is deposited to serve as a negative electrode and a negative current collector film, so that the preparation of the all-solid-state fluorine ion battery is completed.
The anode current collector is a metal film, the anode current collector is prepared by deposition by respectively taking hydrogen and precursors of Sn, Cu, In, Ag or Ti metals as raw materials by adopting an atomic layer deposition method, and the thickness of the deposited film is controlled to be between 0.02 and 0.1 mu m by adjusting the dosage, reaction and cleaning time parameters of each precursor In the atomic layer deposition process.
The positive active substance is a metal fluoride film, and SnF is respectively used by adopting an atomic layer deposition method2、CuF2、InF3、SrF2、YF3Or FeF3Precursors corresponding to the fluoride are used as raw materials for deposition preparation, and the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of the deposited film between 0.02 and 0.1 mu m.
The solid electrolyte is a binary or ternary fluoride film, and BaF is respectively used by adopting an atomic layer deposition method2、CaF2、LaF3Or La1-xBaxF3-x、Ba1-xCaxF2Precursor corresponding to fluoride capable of serving as electrolyte is used as raw material for deposition preparation, and dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of the deposited filmIs made between 0.02 μm and 0.1 μm.
The negative electrode and the negative electrode current collector are metal films, hydrogen and precursors of Al, Mg and Ce are respectively used as raw materials to carry out deposition preparation by adopting an atomic layer deposition method, and the thickness of the deposited film is controlled between 0.02 mu m and 0.1 mu m by adjusting the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process.
The invention has the beneficial effects that: the ionic conductivity of the all-solid-state fluorine ion battery prepared by the method can reach 10-5～10-4S/cm; after 100 times of charging and discharging, the capacity retention rate is still more than 95%.
Detailed Description
In order to further understand the contents, features and effects of the present invention, the following examples are illustrated, and the following detailed descriptions are given:
the preparation method of the all-solid-state fluorine ion battery based on atomic layer deposition is characterized in that glass or silicon wafers are used as substrates, metal films are sequentially deposited by adopting the atomic layer deposition method to serve as a positive current collector, a metal fluoride film is deposited to serve as a positive active substance, a fluoride film is deposited to serve as a solid electrolyte, and a metal film is deposited to serve as a negative electrode and a negative current collector film, so that the preparation of the all-solid-state fluorine ion battery is completed.
The anode current collector is a metal film, the anode current collector is prepared by deposition by respectively taking hydrogen and precursors of Sn, Cu, In, Ag or Ti metals as raw materials by adopting an atomic layer deposition method, and the thickness of the deposited film is controlled to be between 0.02 and 0.1 mu m by adjusting the dosage, reaction and cleaning time parameters of each precursor In the atomic layer deposition process.
The positive active substance is a metal fluoride film, and SnF is respectively used by adopting an atomic layer deposition method2、CuF2、InF3、SrF2、YF3Or FeF3Precursors corresponding to the fluoride are used as raw materials for deposition preparation, and the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of the deposited film between 0.02 and 0.1 mu m.
The solid electrolyteIs a binary or ternary fluoride film, and is prepared by respectively using BaF and BaF through an atomic layer deposition method2、CaF2、LaF3Or La1-xBaxF3-x、Ba1-xCaxF2Precursors corresponding to fluoride capable of serving as electrolyte are used as raw materials for deposition preparation, and the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of a deposited film to be between 0.02 and 0.1 mu m.
The negative electrode and the negative electrode current collector are metal films, hydrogen and precursors of Al, Mg and Ce are respectively used as raw materials to carry out deposition preparation by adopting an atomic layer deposition method, and the thickness of the deposited film is controlled between 0.02 mu m and 0.1 mu m by adjusting the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process.
The invention adopts a closed continuous atomic layer deposition system to sequentially deposit a positive current collector film, a positive active material film, a solid electrolyte film, a negative electrode and a negative current collector film; the system comprises a working chamber and a gas supply device 1#-8#Eight precursor gas sources, wherein each precursor gas source is connected with the working chamber through a pipeline; and controlling the types of precursor gas sources connected into the chamber in each deposition stage and time parameters of the precursor gas sources such as dosage, reaction, cleaning and the like through a Vi program based on Labview.
Example 1
1. Preparing a positive current collector film:
silicon wafer as a substrate, fixed in a chamber of an atomic layer deposition system, using Cu (dmap)2And ZnEt2For the precursor source, deposition of Cu thin films was performed on silicon wafers. The deposition parameters were: cu (dmap)2Dosage 0.2s, reaction 20s, washing 20s, ZnEt2Dosage is 0.2s, reaction is 25s, and washing is 20 s; the reaction temperature is 110 ℃; the thickness is controlled at 0.05 μm. After the reaction, the chamber was flushed by an empty cycle.
2. Preparation of positive electrode active material film:
keeping the silicon wafer substrate in the chamber unchanged, not opening the chamber, replacing the precursor source with Cu (thd)2And TiF4CuF for precursor Source2And (4) depositing a thin film. The deposition parameters were: cu (thd)2Dose 0.4s, response 15s, wash 15s, TiF4The dosage is 0.4s, the reaction is 15s, and the cleaning is 15 s; the reaction temperature is 200 ℃; the thickness is controlled at 0.07 μm. After the reaction, the chamber was flushed by an empty cycle.
3. Preparation of fluoride solid electrolyte film:
holding the silicon wafer substrate in the chamber, not opening the chamber, replacing the precursor source with La (thd)3And TiF4LaF for precursor Source3And (4) depositing a thin film. The deposition parameters were: la (thd)3Dose 0.3s, reaction 20s, wash 15s, TiF4The dosage is 0.2s, the reaction time is 20s, and the cleaning time is 15 s; the reaction temperature is 250 ℃; the thickness is controlled at 0.1 μm. After the reaction, the chamber was flushed by an empty cycle.
4. Preparing a negative electrode and a negative electrode current collector film:
keeping the silicon wafer substrate unchanged in the chamber, replacing the precursor source without opening the chamber, and depositing the Al film by taking trimethylaluminum and hydrogen plasma as the precursor source. The deposition parameters were: TMA dose 0.2s, reaction 10s, Wash 15s, H2The dosage is 0.5s, the reaction time is 20s, the cleaning time is 15s, and the microwave power is 250W; the reaction temperature is 100 ℃; the thickness is controlled at 0.05 μm. After the reaction, the chamber was flushed by an empty cycle.
5. Testing of electrochemical performance of the battery:
the ionic conductivity of the cell was tested using an electrochemical workstation and was 6.3X 10-5S/cm. After the battery is charged and discharged for 100 times, the capacity retention rate is 97.3%.
Example 2
1. Preparing a positive current collector film:
glass slides were mounted in the atomic layer deposition system chamber using Cu (dmap)2And ZnEt2For precursor source, deposition of Cu thin film was performed on the slide. The deposition parameters were: cu (dmap)20.1s dosage, 15s reaction, 30s washing, ZnEt2The dosage is 0.1s, the reaction is 20s, and the cleaning is 30 s; reaction temperatureIs 110 ℃; the thickness is controlled at 0.02 μm. After the reaction, the chamber was flushed by an empty cycle.
2. Preparation of positive electrode active material film:
holding the slide substrate in the chamber, not opening the chamber, replacing the precursor source with Cu (thd)2And TiF4CuF for precursor Source2And (4) depositing a thin film. The deposition parameters were: cu (thd)2Dose 0.2s, reaction 20s, wash 25s, TiF4Dosage is 0.15s, reaction is 20s, and cleaning is 25 s; the reaction temperature is 200 ℃; the thickness is controlled at 0.02 μm. After the reaction, the chamber was flushed by an empty cycle.
3. Preparation of fluoride solid electrolyte film:
holding the slide substrate in the chamber, not opening the chamber, replacing the precursor source with La (thd)3And TiF4LaF for precursor Source3And (4) depositing a thin film. The deposition parameters were: la (thd)3Dose 0.1s, reaction 20s, wash 15s, TiF4The dosage is 0.1s, the reaction time is 20s, and the cleaning time is 15 s; the reaction temperature is 250 ℃; the thickness is controlled at 0.05 μm. After the reaction, the chamber was flushed by an empty cycle.
4. Preparing a negative electrode and a negative electrode current collector film:
keeping the glass slide substrate unchanged in the chamber, changing the precursor source without opening the chamber, and depositing the Al film by taking trimethyl aluminum and hydrogen plasma as the precursor source. The deposition parameters were: TMA dose 0.1s, reaction 15s, Wash 20s, H2The dosage is 0.3s, the reaction time is 20s, the cleaning time is 25s, and the microwave power is 250W; the reaction temperature is 100 ℃; the thickness is controlled at 0.02 μm. After the reaction, the chamber was flushed by an empty cycle.
5. Testing of electrochemical performance of the battery:
the ionic conductivity of the cell was tested using an electrochemical workstation and was 1.2X 10-4S/cm. After the battery is charged and discharged for 100 times, the capacity retention rate is 96.1%.
Example 3
1. Preparing a positive current collector film:
with glass slides as liningsA base, secured within a chamber of an atomic layer deposition system, employing Cu (dmap)2And ZnEt2For precursor source, deposition of Cu thin film was performed on the slide. The deposition parameters were: cu (dmap)2Dosage of 0.3s, reaction of 30s, washing of 40s, ZnEt2Dosage is 0.35s, reaction is 35s, and cleaning is 40 s; the reaction temperature is 110 ℃; the thickness is controlled at 0.1 μm. After the reaction, the chamber was flushed by an empty cycle.
2. Preparation of positive electrode active material film:
holding the slide substrate in the chamber, not opening the chamber, replacing the precursor source with Cu (thd)2And TiF4CuF for precursor Source2And (4) depositing a thin film. The deposition parameters were: cu (thd)2Dose 0.65s, response 25s, wash 30s, TiF4The dosage is 0.5s, the reaction is 25s, and the cleaning is 30 s; the reaction temperature is 200 ℃; the thickness is controlled at 0.1 μm. After the reaction, the chamber was flushed by an empty cycle.
3. Preparation of fluoride solid electrolyte film:
holding the slide substrate in the chamber, not opening the chamber, replacing the precursor source with La (thd)3And TiF4LaF for precursor Source3And (4) depositing a thin film. The deposition parameters were: la (thd)3Dose 0.4s, response 30s, wash 35s, TiF4Dosage is 0.3s, reaction is 30s, and cleaning is 35 s; the reaction temperature is 250 ℃; the thickness is controlled at 0.1 μm. After the reaction, the chamber was flushed by an empty cycle.
4. Preparing a negative electrode and a negative electrode current collector film:
keeping the glass slide substrate unchanged in the chamber, changing the precursor source without opening the chamber, and depositing the Al film by taking trimethyl aluminum and hydrogen plasma as the precursor source. The deposition parameters were: TMA dose 0.3s, reaction 20s, wash 35s, H2The dosage is 0.5s, the reaction time is 30s, the cleaning time is 35s, and the microwave power is 250W; the reaction temperature is 100 ℃; the thickness is controlled at 0.1 μm. After the reaction, the chamber was flushed by an empty cycle.
5. Testing of electrochemical performance of the battery:
detachment of cells using electrochemical workstationThe sub-conductivity was measured and found to be 2.7X 10-5S/cm. After the battery is charged and discharged for 100 times, the capacity retention rate is 95.1%.
The above-mentioned embodiments are only for illustrating the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and to carry out the same, and the present invention shall not be limited to the embodiments, i.e. the equivalent changes or modifications made within the spirit of the present invention shall fall within the scope of the present invention.
Claims (3)
1. A preparation method of an all-solid-state fluorine ion battery based on atomic layer deposition is characterized in that glass or silicon wafers are used as substrates, metal films are sequentially deposited by adopting the atomic layer deposition method to serve as a positive current collector, a metal fluoride film is deposited to serve as a positive active substance, the fluoride film is deposited to serve as a solid electrolyte, the metal films are deposited to serve as a negative electrode and a negative current collector film, and the preparation of the all-solid-state fluorine ion battery is completed;
the positive active substance is a metal fluoride film, and SnF is respectively used by adopting an atomic layer deposition method2、CuF2、InF3、SrF2、YF3Or FeF3Precursor corresponding to fluoride is used as raw material to carry out deposition preparation, and the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of the deposited film between 0.02 mu m and 0.1 mu m;
the solid electrolyte is a binary or ternary fluoride film, and BaF is respectively used by adopting an atomic layer deposition method2、CaF2、LaF3Or La1-xBaxF3-x、Ba1-xCaxF2Precursors corresponding to fluoride capable of serving as electrolyte are used as raw materials for deposition preparation, and the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process are adjusted to control the thickness of a deposited film to be between 0.02 and 0.1 mu m.
2. The method for preparing an all-solid-state fluoride ion battery based on atomic layer deposition according to claim 1, wherein the positive electrode current collector is a metal thin film, the anode current collector is prepared by deposition by using hydrogen and one or more of Sn, Cu, In, Ag and Ti as raw materials by an atomic layer deposition method, and the thickness of the deposited thin film is controlled to be between 0.02 μm and 0.1 μm by adjusting the dosage, reaction and cleaning time parameters of each precursor during the atomic layer deposition.
3. The method for preparing the all-solid-state fluoride ion battery based on the atomic layer deposition according to claim 1, wherein the negative electrode and the negative electrode current collector are metal films, the atomic layer deposition method is adopted to respectively perform deposition preparation by using hydrogen and precursors of any one or a combination of several of Al, Mg and Ce as raw materials, and the thickness of the deposited film is controlled between 0.02 μm and 0.1 μm by adjusting the dosage, reaction and cleaning time parameters of each precursor in the atomic layer deposition process.
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