CN117832412A - Positive electrode material for solid electrolyte molten lithium metal battery - Google Patents
Positive electrode material for solid electrolyte molten lithium metal battery Download PDFInfo
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- CN117832412A CN117832412A CN202211178536.3A CN202211178536A CN117832412A CN 117832412 A CN117832412 A CN 117832412A CN 202211178536 A CN202211178536 A CN 202211178536A CN 117832412 A CN117832412 A CN 117832412A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 48
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 39
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 37
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 44
- 239000002482 conductive additive Substances 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 16
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000007769 metal material Substances 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims description 14
- 239000000654 additive Substances 0.000 claims description 12
- 230000000996 additive effect Effects 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 2
- -1 lithium halides Chemical class 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000002844 melting Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 2
- 239000004020 conductor Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000011701 zinc Substances 0.000 abstract description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052802 copper Inorganic materials 0.000 abstract description 6
- 239000010949 copper Substances 0.000 abstract description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 abstract description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052797 bismuth Inorganic materials 0.000 abstract description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052793 cadmium Inorganic materials 0.000 abstract description 4
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052804 chromium Inorganic materials 0.000 abstract description 4
- 239000011651 chromium Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 239000010936 titanium Substances 0.000 abstract description 4
- 229910052719 titanium Inorganic materials 0.000 abstract description 4
- 229910052725 zinc Inorganic materials 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 14
- 239000010405 anode material Substances 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910021525 ceramic electrolyte Inorganic materials 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 7
- 229910003002 lithium salt Inorganic materials 0.000 description 6
- 159000000002 lithium salts Chemical class 0.000 description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000002238 carbon nanotube film Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 3
- 229910013618 LiCl—KCl Inorganic materials 0.000 description 2
- 241000219991 Lythraceae Species 0.000 description 2
- 235000014360 Punica granatum Nutrition 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000003411 electrode reaction Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 241000283070 Equus zebra Species 0.000 description 1
- 229910015475 FeF 2 Inorganic materials 0.000 description 1
- 229910010238 LiAlCl 4 Inorganic materials 0.000 description 1
- YFXWODPYUNGUEE-UHFFFAOYSA-N [I].[Li] Chemical compound [I].[Li] YFXWODPYUNGUEE-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- LYQFWZFBNBDLEO-UHFFFAOYSA-M caesium bromide Inorganic materials [Br-].[Cs+] LYQFWZFBNBDLEO-UHFFFAOYSA-M 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- ZVSWQJGHNTUXDX-UHFFFAOYSA-N lambda1-selanyllithium Chemical compound [Se].[Li] ZVSWQJGHNTUXDX-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- 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
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
-
- 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
Abstract
A positive electrode material for a solid electrolyte molten lithium metal battery, the positive electrode material comprising an active metal material selected from any one or more metal simple substances or alloys of the metal simple substances of aluminum, titanium, chromium, manganese, iron, nickel, copper, zinc, cadmium, lead and bismuth, an active lithium source selected from one or a mixture of LiF and LiCl, and a conductive additive and a lithium ion conductive additive.
Description
Technical Field
The application relates to the technical field of solid electrolyte molten lithium metal batteries, in particular to a positive electrode material for a solid electrolyte molten lithium metal battery.
Background
Both electric vehicles and electric network energy storage require batteries with high safety, low cost and high energy density, and the existing battery technology is difficult to meet all requirements, so that new batteries need to be improved or developed. The solid electrolyte molten lithium metal battery developed in recent years has the structural characteristics and the performance characteristics of advanced batteries such as a solid lithium battery, a lithium metal battery, a sodium-sulfur battery, a ZEBRA battery and the like, and is expected to meet the practical application requirements of energy storage of electric automobiles and power grids.
CN202210022945.8 discloses a high-temperature molten lithium-iodine battery based on a pomegranate Dan Gutai electrolyte, which comprises a pomegranate Dan Gutai electrolyte, a positive electrode material and a negative electrode material, wherein the positive electrode material comprises a CsI/LiI eutectic salt.
CN202010821748.3 discloses a lithium-free dendrite anode of a carbon nanotube film directly composited with molten lithium metal, which is characterized in that: through heat exchange between the carbon nano tube and the environment, a temperature gradient exists in the direction vertical to the surface of the material, and the temperature gradient is regulated and controlled to enable the liquid lithium metal and the upper carbon nano tube film to generate negative Gibbs free energy, so that the liquid lithium metal is driven to infiltrate into the upper carbon nano tube film; the liquid lithium is directly and evenly coated or infused into a composite material formed by a carbon nano tube film, so that the lithium-free dendrite lithium metal battery anode with a three-dimensional nano structure is obtained.
CN201980092766.8 discloses a high energy density molten lithium sulfur and lithium selenium battery with a solid electrolyte, which can be prepared by combining together a molten S or Se (or mixtures thereof) anode, a molten lithium cathode and a solid electrolyte, for example from Li 6.4 La 3 Zr 1.4 Ta 0.6 O 12 (LLZTO) composition capable of conducting lithium ions.
The invention provides a novel anode material for a solid electrolyte molten lithium metal battery, which has good electrochemical performance and lower energy cost, and can further improve the comprehensive performance of the battery.
Disclosure of Invention
The invention discloses a positive electrode material for a solid electrolyte molten lithium metal battery, which comprises an active metal material, wherein the active metal material is selected from any one or more metal simple substances or alloys of the metal simple substances in aluminum, titanium, chromium, manganese, iron, nickel, copper, zinc, cadmium, lead and bismuth, the active lithium source is selected from one or a mixture of LiF and LiCl, and a conductive additive and a lithium ion conductive additive. The active metal material, lithium source, conductive additive and lithium ion conductive additive contained in the positive electrode material are all commonly used powder substances. The materials have the advantages of wide sources, easy acquisition, no pollution to the environment, convenient transportation, low price and the like.
A positive electrode material for a solid electrolyte molten lithium metal battery, the positive electrode material consisting of an active metal, an active lithium source, and a conductive additive and a lithium ion conducting additive, wherein the active lithium source is selected from one or a mixture of lithium halides.
Further, the positive electrode composed of the active metal material has a theoretical mass energy density of more than 500Wh/kg, or more than 700Wh/kg, or more than 1000Wh/kg, or more than 1200Wh/kg when only active materials are calculated; the theoretical volumetric energy density is greater than 1500Wh/L, or greater than 2000Wh/L, or greater than 3000Wh/L, or greater than 5000Wh/L; the energy cost of the battery is lower than 600 yuan/kWh; the capacity utilization of the battery is greater than 60%, alternatively greater than 70%, alternatively greater than 75%.
Further, the positive electrode material comprises an active metal material selected from any one or more metal simple substances or alloys of the metal simple substances of aluminum, titanium, chromium, manganese, iron, nickel, copper, zinc, cadmium, lead and bismuth.
Further, the active lithium source is selected from one or a mixture of LiF and LiCl.
Further, the conductive additive material has good conductivity at 200-400 ℃ and electronic conductivity>0.1S/m; has good chemical stability and oxidation potential higher than 2.5VvsLi + /Li。
Further, the conductive additive material is selected from one or more of graphite, carbon black, acetylene, amorphous carbon, carbon fiber, carbon nano tube, graphene, copper powder, copper mesh and foam copper, so as to construct a three-dimensional conductive sub-network.
Further, the lithium ion conductive additive material is inorganic salt or mixed salt, has a certain solubility to LiCl or LiF in a molten state, has a melting point lower than 400 ℃ and has an oxidative decomposition potential higher than 2.5VvsLi + /Li。
Further, the lithium ion conductive additive material is selected from LiAlCl 4 、NaAlCl 4 、LiCl-KCl、LiBr-KBr、LiI-CsI、LiCl-ZnCl 2 、NaCl-ZnCl 2 、KCl-ZnCl 2 Or LiBr-KBr-CsBr for transporting Li + 。
When preparing the positive electrode material, firstly preparing the lithium ion conducting additive (such as LiCl-KCl mixed salt), and then weighing the lithium ion conducting additive as a whole according to the proportion and adding the lithium ion conducting additive into the positive electrode material.
Further, the positive electrode material consists of active metal M (M is any one or more metal simple substances or alloys of the metal simple substances of aluminum, titanium, chromium, manganese, iron, nickel, copper, zinc, cadmium, lead and bismuth), lithium source LiX (LiX is LiF, liCl or a mixture of the LiF and the LiCl), a conductive additive and a lithium ion conductive additive.
Further, the molar ratio of active metal to lithium source (lithium salt) is 1 (1-4), which may be, for example, 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, or 1:4.
Further, the mass ratio of the lithium source (lithium salt) to the electron-conducting additive is (0.1-10): 1, for example, may be 0.1:1, 0.2:1, 0.5:1, 1:1, 2:1, 5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, or 10:1.
Further, the mass ratio of the lithium source (lithium salt) to the ion conducting additive is 1 (0.1-5), for example, may be 1:0.1, 1:0.5, 1:1, 1:1.5, 1:2, 1:2.5, 1:3, 1:3.2, 1:3.4, 1:3.6, 1:3.8, 1:4, 1:4.5 or 1:5.
Wherein, the optimal molar ratio of the active metal to the lithium salt is 1:n, wherein n is the valence of metal ions generated by the active metal discharge; the optimal ratio of the lithium salt to the conductive additive is 5:1, and the optimal ratio of the lithium salt to the conductive additive is 1:1.5.
The positive electrode material has higher energy density, and theoretical mass energy density is more than 500Wh/kg, or more than 700Wh/kg, or more than 1000Wh/kg, or more than 1200Wh/kg, and theoretical volume energy density is more than 1500Wh/L, or more than 2000Wh/L, or more than 3000Wh/L, or more than 5000Wh/L.
The invention also provides a preparation method of the anode material, which comprises the step of ball milling the active metal, the active lithium source, the conductive additive and the lithium ion conductive additive to obtain the uniform anode material.
The invention also provides application of the positive electrode material in a solid electrolyte molten lithium metal battery, wherein the solid electrolyte molten lithium metal battery comprises a positive electrode, a negative electrode and a solid electrolyte.
Further, the solid electrolyte is an LLZTO ceramic tube.
The structure of a solid electrolyte molten lithium metal battery using the positive electrode material of the present invention is shown in fig. 1, and the solid electrolyte is a U-shaped ceramic tube.
The principle of the battery is as follows:
the positive electrode is densely filled outside the U-shaped ceramic tube by using the positive electrode material, the inside of the ceramic tube is used as the negative electrode of the battery, and the negative electrode is assembled in a discharge state without pre-filling metal Li.
In addition, the Li is led in the positive electrode material + Molten salt with transport Li + The positive electrode material always keeps close contact with the U-shaped ceramic tube during the charge and discharge process of the battery under the action of ions so as to facilitate Li + And (3) ion transmission.
When charged, M in the positive electrode loses n (n is 2,3 or 4) electrons to generate M n+ And with X in the positive electrode - Combining to generate MX n . At the same time, li in the positive electrode + Electrons are obtained in the negative electrode through the U-shaped ceramic tube, and elemental metal Li is generated.
During discharge, elemental Li metal in the anode loses electrons, and generated Li + X-is combined with LiX in the positive electrode through the U-shaped ceramic tube, and meanwhile M n+ N electrons are obtained, generating M.
Further, the reaction formula of the battery is:
positive electrode reaction: MX (MX) n +nLi + +ne→M+nLiX
Negative electrode reaction: nLi → nLi + +ne
Total reaction: MX (MX) n +nLi→M+nLiX
Further, the battery is operated at a temperature of 100-800 ℃ during charge-discharge cycles, preferably the battery is operated at a temperature of 200-400 ℃.
The invention has the following advantages:
(1) The anode material has no inflammable, explosive, volatile and gas-producing components and high safety.
(2) The positive electrode material has higher energy density, theoretical mass energy density is more than 500Wh/kg, and theoretical volume energy density is more than 1500Wh/L.
(3) The preparation process of the anode material is simple, the source of raw materials is wide, the anode material is cheaper, and the theoretical energy cost is lower than 600 yuan/kWh.
(4) The lithium ion passage and the electron passage in the positive electrode material are smooth, so that the active substances can fully react, and the capacity exertion rate is more than 60%.
Drawings
The foregoing and/or additional aspects and advantages of the present application will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings, wherein:
fig. 1 is a schematic diagram of a solid electrolyte molten lithium metal battery of the present patent, wherein (1) is a seal, (2) is a stainless steel case, (3) is a solid electrolyte, (4) is a current collector, (5) is a negative electrode region, and (6) is a positive electrode region.
Fig. 2 is a charge curve of a solid electrolyte molten lithium metal battery in example 1.
Fig. 3 is a charge curve of a solid electrolyte molten lithium metal battery in example 2.
Fig. 4 is a charge curve of a solid electrolyte molten lithium metal battery in example 3.
Fig. 5 is a discharge curve of the solid electrolyte molten lithium metal battery of example 4.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the present application, and the terminology used is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments based on the present application.
Some detailed embodiments of the present invention will be disclosed below, although examples of implementation are described in this disclosure, embodiments of the present invention are not limited to what has been shown. The disclosed embodiments are merely examples of what may be claimed as examples of what may be provided and other embodiments that are not shown and alternatives, modifications, equivalents, etc. may be included within the scope of the claims.
Example 1
0.87g of Zn simple substance powder, 1.12g of LiCl powder, copper powder accounting for 50 percent of the mass of LiCl, naCl-ZnCl accounting for 100 percent of the mass of LiCl 2 (NaCl 0.19g, znCl) 2 0.93 g) are put into a high-energy ball mill together, ball milling is uniform, and a uniform anode material is obtained.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. Li in molten ion-conducting additive when the battery is charged + Ions can pass through LLZTO ceramic electrolyte to reach the cathode and combine with electrons from an external circuit to form a Li cathode, and meanwhile Cl-reacts with Zn to generate ZnCl 2 And release electrons to the external circuit. The reverse process is carried out during discharge, and Li in the negative electrode loses electrons to form Li + ，Li + Returns to the positive electrode through the ceramic electrolyte.
Fig. 2 is a charge curve of a solid electrolyte molten lithium metal battery in example 1.
Example 2
1.12g of Zn simple substance powder, 1.46g of LiCl powder, graphite powder accounting for 20 percent of the mass of LiCl and LiAlCl accounting for 150 percent of the mass of LiCl are mixed 4 Putting the materials together into a high-energy ball mill, and uniformly ball-milling to obtain a uniform anode material.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. Li in molten ion-conducting additive when the battery is charged + Ions can pass through LLZTO ceramic electrolyte to reach the cathode and combine with electrons from an external circuit to form a Li cathode, and meanwhile Cl-reacts with Zn to generate ZnCl 2 And release electrons to the external circuit. The reverse process is carried out during discharge, and Li in the negative electrode loses electrons to form Li + ，Li + Returns to the positive electrode through the ceramic electrolyte.
Fig. 3 is a charge curve of a solid electrolyte molten lithium metal battery of example 2.
Example 3
0.72g of Ni simple substance powder, 1.04g of LiCl powder, carbon black powder accounting for 20 percent of the mass of LiCl and NaAlCl accounting for 250 percent of the mass of LiCl 4 Putting the materials together into a high-energy ball mill, and uniformly ball-milling to obtain a uniform anode material.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. Li in molten ion-conducting additive when the battery is charged + Ions will pass through LLZTO ceramic electrolyte to reach the anode and combine with electrons from the external circuit to form Li anode, while Cl-reacts with Ni to form NiCl 2 And release electrons to the external circuit. The reverse process is carried out during discharge, and Li in the negative electrode loses electrons to form Li + ，Li + Returns to the positive electrode through the ceramic electrolyte.
Fig. 4 is a charge curve of a solid electrolyte molten lithium metal battery in example 3.
Example 4
2.08g of Fe simple substance powder, 1.94g of LiF powder, 10 percent of graphite powder accounting for LiF mass and 150 percent of KCl-ZnCl accounting for LiF mass 2 (KCl 0.91g, znCl) 2 2.00 g) are put into a high-energy ball mill together, ball milling is uniform, and a uniform anode material is obtained.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. Li in molten ion-conducting additive when the battery is charged + Ions can pass through LLZTO ceramic electrolyte to reach the cathode and combine with electrons from an external circuit to form a Li cathode, and F-reacts with Fe to generate FeF 2 And release electrons to the external circuit. The reverse process is carried out during discharge, and Li in the negative electrode loses electrons to form Li + ，Li + Returns to the positive electrode through the ceramic electrolyte.
Fig. 5 is a discharge curve of the solid electrolyte molten lithium metal battery of example 4.
Table 1 product performance tables for examples 1-4
Comparative example 1:
0.87g of Zn simple substance powder, 1.12g of LiCl powder, copper powder accounting for 50 percent of the mass of LiCl, naCl-ZnCl accounting for 5 percent of the mass of LiCl 2 (NaCl 0.0095g, znCl) 2 0.0465 g) were put into a high-energy ball mill together, and ball-milled uniformly to obtain a uniform cathode material.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. The battery cannot be charged or discharged, and the capacity utilization rate is 0%.
Comparative example 2:
1.12g of Zn simple substance powder, 1.46g of LiCl powder, 1400% of graphite powder based on the mass of LiCl and 150% of LiAlCl based on the mass of LiCl 4 Putting the materials together into a high-energy ball mill, and uniformly ball-milling to obtain a uniform anode material.
The positive electrode is made of positive electrode material, the negative electrode is only provided with a current collector, and an LLZTO ceramic tube is selected as a solid electrolyte. The battery can be charged and discharged, but the capacity utilization rate is only 9.47%.
Claims (9)
1. A positive electrode material for a solid electrolyte molten lithium metal battery, the positive electrode material comprising an active metal, an active lithium source, and a conductive additive and a lithium ion conducting additive, wherein the active lithium source is selected from one or a mixture of lithium halides, and the capacity utilization rate of the battery is greater than 60%.
2. The positive electrode material according to claim 1, characterized in that the positive electrode composed of the active metal material has a theoretical mass energy density of more than 500Wh/kg, or more than 700Wh/kg, or more than 1000Wh/kg, or more than 1200Wh/kg, when only active substances are calculated; the theoretical volumetric energy density is greater than 1500Wh/L, or greater than 2000Wh/L, or greater than 3000Wh/L, or greater than 5000Wh/L.
3. The positive electrode material according to claim 1 or 2, wherein the active lithium source is selected from one or a mixture of LiF and LiCl.
4. A positive electrode material according to claims 1 to 3, wherein the electron conductor additive material has good electrical conductivity, electron conductivity at 200-400 °c>0.1S/m, oxidation potential higher than 2.5V vs Li + /Li。
5. The positive electrode material according to any one of claims 1 to 4, wherein the lithium ion conductive additive material is an inorganic salt or a mixed salt, has a solubility to LiCl or LiF in a molten state, has a melting point of less than 400 ℃, and has an oxidative decomposition potential of more than 2.5V vs Li + /Li。
6. The method for preparing a positive electrode material according to any one of claims 1 to 5, comprising ball milling an active metal, an active lithium source, and a conductive additive with a lithium ion conductive additive to obtain a uniform positive electrode material.
7. The positive electrode material prepared by the preparation method according to claim 6.
8. Use of the positive electrode material according to claims 1 to 4, 7 in a solid electrolyte molten lithium metal battery comprising a positive electrode, a negative electrode, a solid electrolyte.
9. The use according to claim 8, wherein the solid electrolyte is LLZTO ceramic tube.
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| CN202211178536.3A CN117832412A (en) | 2022-09-27 | 2022-09-27 | Positive electrode material for solid electrolyte molten lithium metal battery |
| PCT/CN2023/121841 WO2024067659A1 (en) | 2022-09-27 | 2023-09-27 | Cathode material for solid-state electrolyte molten lithium battery |
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