CN116936920A - Halide solid electrolyte material with metastable phase structure, and preparation method and application thereof - Google Patents
Halide solid electrolyte material with metastable phase structure, and preparation method and application thereof Download PDFInfo
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- 150000004820 halides Chemical class 0.000 title claims abstract description 119
- 239000000463 material Substances 0.000 title claims abstract description 102
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 72
- 239000002001 electrolyte material Substances 0.000 claims abstract description 29
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 150000001768 cations Chemical class 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 9
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 9
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 7
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 4
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 4
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 4
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 3
- 238000000498 ball milling Methods 0.000 claims description 29
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 11
- 238000002441 X-ray diffraction Methods 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- -1 carrier ions Chemical class 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000470 constituent Substances 0.000 claims description 4
- 230000014759 maintenance of location Effects 0.000 claims description 4
- 229910052727 yttrium Inorganic materials 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000007774 positive electrode material Substances 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002000 Electrolyte additive Substances 0.000 claims description 2
- 238000001069 Raman spectroscopy Methods 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000005259 measurement Methods 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000013307 optical fiber Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- 230000001747 exhibiting effect Effects 0.000 claims 1
- 239000007773 negative electrode material Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000006872 improvement Effects 0.000 abstract description 4
- 238000013329 compounding Methods 0.000 abstract description 3
- 239000006104 solid solution Substances 0.000 abstract description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 36
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 34
- 229910007926 ZrCl Inorganic materials 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 29
- 238000007789 sealing Methods 0.000 description 9
- 239000012535 impurity Substances 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 229910001507 metal halide Inorganic materials 0.000 description 4
- 150000005309 metal halides Chemical class 0.000 description 4
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- 230000000739 chaotic effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 2
- 229910021617 Indium monochloride Inorganic materials 0.000 description 2
- 229910013716 LiNi Inorganic materials 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- APHGZSBLRQFRCA-UHFFFAOYSA-M indium(1+);chloride Chemical compound [In]Cl APHGZSBLRQFRCA-UHFFFAOYSA-M 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910016569 AlF 3 Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910015965 LiNi0.8Mn0.1Co0.1O2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000001815 facial effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000002203 sulfidic glass Substances 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 238000012795 verification 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
- H01M10/056—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
- 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
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The application discloses a halide solid electrolyte material with a metastable phase structure, a preparation method and application thereof, and an electrolyte material A-M1M2-X; wherein X is halogen, including one or more than two of F, cl, br, I; a is a carrier and comprises one or more than two of Li, na, K, cu, ag, mg ions; m1 is a rare earth element, and comprises one or more than two of La, ce and Sm; m2 is doped metal, satisfying: the coordination number difference between M1 and M2 is more than or equal to 1.15; the difference of the ionic radius of M1 and M2 is more than or equal to 1.25 according to the calculation of the crystallographic ionic radius. The structural effect of high confusion and high internal energy generated by doping, solid solution or compounding of a plurality of cations M2 with large structural difference with M1 is adopted to carry out structural modification on A-M1-X, so that the improvement of ion conduction rate, air stability and the like is realized.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a halide solid electrolyte material with a metastable phase structure, and a preparation method and application thereof.
Background
The development of solid electrolyte with high ionic conductivity, wide electrochemical stability window and controllable cost is key to realizing the practical application of all solid-state battery. The halide solid electrolyte has gained high attention in academia and industry because of the advantages of high oxidation stability, no toxic gas release by reaction with air, and the like.
The related art literature shows that: halide solid state electrolyte conducting Li + The ion modes mainly comprise three types: 1. having halogen anions (Cl) - 、Br - 、I - ) Crystalline phase halide solid state electrolyte, li, which is densely packed to form transport channels + Ions are transported along "octahedral-tetrahedral-octahedral" channels or "octahedral-octahedral" channels, e.g. Li 3 InCl 6 (patent document: CN 111916820A); 2. with UCl 3 Crystalline phase halide solid state electrolyte of lattice transport channel, li + The ions are mainly conducted in one-dimensional channels surrounded by co-sided three-cap triangular prisms, e.g. Li 0.388 Ta 0.238 La 0.475 Cl 3 (patent document: CN 113772729A); 3. composite solid electrolytes composed of oxides and halides, with li+ ions transported predominantly at the interface of the halide grains and oxide grains, e.g. LiBH 4 -LiI/Al 2 O 3 (non-patent document: 10.1021/acsami.0c10361).
However, the halide solid-state electrolyte disclosed in the related art document has some bottleneck problems:
1. ion conductivity (e.g., li) 3 InCl 6 About 1.36×10 -3 S cm -1 ) Still not high enough, and difficult to service at very low temperatures (-30 ℃).
2. The inclusion of expensive metallic elements, including Sc, Y, in, ta, results in high raw material costs. Limiting the application of halide electrolyte materials.
3. The air stability is insufficient, and it is difficult to use the air conditioner in an environment including a drying room.
Disclosure of Invention
The technical problems to be solved by the application are as follows: the application provides a novel electrolyte material with higher ionic conductivity and higher air stability, and provides a halide solid electrolyte material with a metastable phase structure, a preparation method and application thereof.
The application is realized by the following technical scheme:
a halide solid electrolyte material having a metastable phase structure,
electrolyte material a-M1M2-X, wherein:
x is halogen, including one or more than two of F, cl, br, I;
a is a carrier and is one or the combination of more than two of Li, na, K, cu, ag, mg ions;
m1 is a rare earth element, and comprises one or more than two of La, ce and Sm;
m2 is doped metal, satisfying: the coordination number difference between M1 and M2 is more than or equal to 1.15; the difference of the ionic radius of M1 and M2 is more than or equal to 1.25 according to the calculation of the crystallographic ionic radius.
The halide electrolyte material provided by the application is a metastable phase structure with high disorder degree and high internal energy and fast ion conduction capability, and the metastable phase structure is obtained by adopting a plurality of cations M2 with large structural difference with M1 to carry out modification on aspects of structural modification, ion conduction rate improvement, air stability improvement and the like on A-M1-X (one or more of X= F, cl, br, I) due to high disorder degree and high internal energy structural effect generated by doping, solid solution or compounding. The A metal ion is a carrier, and M1 is an inexpensive light rare earth element.
The M1 and M2 cations with larger structural difference are inconsistent coordination environments of M1 and M2 in the obtained material structure; the coordination number difference between M1 and M2 is more than or equal to 1.3; according to the calculation of the crystallographic ion radius, the difference of the ion radius between M1 and M2 is more than or equal to 1.25; the difference value calculation is calculated by dividing a large value by a small value by the ratio of the two values.
Further alternatively, M2 comprises a combination of two or more of Ta, zr, hf, al, nb, ga.
Further preferably, the molar ratio of M1 to M2 is c,0.1< c <10; more preferably 0.33< c <3.
Further preferably, when a combination of two or more of La, ce, and Sm is selected for M1, the ratio of the molar amounts of the rare earth elements is preferably 1:1. If two rare earth elements are combined, the ratio of the two rare earth elements is 1:1, and if three rare earth elements are combined, the ratio of the three rare earth elements is 1:1:1.
Further preferably, when two or more metal elements are selected for M2, the molar ratio of the elements is preferably 1:1. For example, when two elements are combined, the ratio of the two elements is 1:2-2:1, more preferably 1:1, and when three elements are combined, the ratio of the three elements is 1:1:1.
Further alternatively, a is a carrier, comprising one or a combination of two or more of Na, K, cu, ag, mg ions; the amount of carrier species is 20% to 75%, preferably 33% to 66% of the total cation content.
In the prior art, only Li lithium ions are generally used. The material provided by the application can realize the ultra-fast ion conduction function not only comprising Li ions but also comprising Na, K, cu, ag, mg ions. The ion conduction rate is improved by several times to more than a plurality of orders of magnitude compared with the structural material with lower degree of disorder.
Further optionally, modifying/doping ions are also included: o, N, P, S, B, H, C, in, yb, Y, ho, zn, or a combination of two or more thereof.
In the material with the metastable state structure, O, N, P, S, B, H, C, in, yb, Y, ho, zn modification, doping and compounding can be further carried out.
In addition, unavoidable impurities may exist in the material provided by the application, the unavoidable impurities include elements which are unintentionally brought in as impurities in the raw material manufacturing and halide solid electrolyte material synthesis processes, and the limitations of the impurities include: rare earth impurity elements are less than or equal to 2.00wt% each, and other impurity elements are less than or equal to 0.20wt%.
Further alternatively, the method may comprise, in a further alternative,
metastable phase structure in X-ray diffraction measurements using copper kα rays:
a diffraction peak at a position of 2θ=13.7° ±0.2°;
and/or, the optical fiber has double diffraction peaks at the positions of 2 theta = 23.7 degrees +/-0.15 degrees to 2 theta = 24.8 degrees +/-0.15 degrees, and the peak intensity ratio is 0.2 to 5; preferably, there is a diffraction peak at the position 2θ=23.8°±0.1°,2θ=24.7°±0.1°;
and/or, a diffraction peak is present at a position of 2θ=31.7° ±0.15°,2θ=34.7° ±0.15°,2θ=42.6° ±0.15°, wherein a multiple diffraction peak is present in the vicinity of the position of 2θ=42.0° ±1.0°.
And/or metastable phase structure in use of 512cm -1 In the raman spectrometer measurement of laser:
sample at retention of LaCl 3 Outside the characteristic vibration peak of (2) at 250-400 cm -1 A broad vibration peak was exhibited in the range. Wherein peak 1 is 210+ -10 cm -1 Position, peak 2 at 340.+ -.10 cm -1 A location; the peak intensity ratio (half-peak width times peak height) of the peak 1 to the peak 2 is defined as a (a=i1/I2, I1 is the half-peak width times peak height of the peak 1, I2 is the half-peak width times peak height of the peak 2), a.ltoreq.5, more preferably a.ltoreq.0.5.
Further optionally, an amorphous phase is included, in which carriers, M1, and a plurality of M2 metal cation elements are mixed;
alternatively, a crystalline phase comprising a portion of the constituent elements in the amorphous phase is also included.
The metastable phase structure comprises an amorphous phase portion. The amorphous internal carrier, M1 and a plurality of M2 metal cation elements are mixed and arranged, the ultra-fast ion conduction rate can be provided, and the maximum room temperature ion conduction rate can reach more than 1S/cm. Further, the effect of high miscibility in the amorphous phase structure is a major cause of ion conduction in this particular metastable phase structure.
Preferably, the metastable phase structure further comprises a crystalline phase comprising a portion of the constituent elements of the amorphous phase, but not exactly the same as the amorphous phase constituent.
In the metastable phase structure, metal ions are distributed in an amorphous phase and a crystalline phase, and are mutually compounded to achieve the effects of stable structure and improved ion conduction rate.
A method for preparing a halide solid electrolyte material having a metastable phase structure, comprising the steps of: one or more of halide, oxide, hydroxide, nitride or oxyhalide compounds of metal cations including carrier ions, M1 ions and M2 ions are mixed and ball-milled by a ball-milling synthesis means.
Preferably, planetary ball mills are used for ball milling.
Preferably, the ball-material ratio is 1:20-1:60, the rotating speed is 200-800 rpm, and the ball milling time is 2-15 h.
After the metastable phase structure is subjected to operations such as heating and annealing to obtain a stable phase, the ion conduction rate of the metastable phase structure is greatly reduced.
Use of a halide solid state electrolyte material having a metastable phase structure, characterized by being applied in a solid state battery; the halide solid electrolyte material is a halide solid electrolyte material with a metastable phase structure or a material prepared by the preparation method of the halide solid electrolyte material with the metastable phase structure.
Further alternatively, the electrolyte material or additive is added to the anode material and the cathode material, and the electrolyte material is used as a solid electrolyte, a solid electrolyte stabilizer, an anode-cathode ion conduction additive or an electrode-electrolyte interface modifier.
A battery, comprising:
a halide solid electrolyte material having a polycation mixed structure, which is a halide solid electrolyte material having a metastable phase structure according to any one of claims 1 to 6, or a material obtained by a process for producing a halide solid electrolyte material having a metastable phase structure according to claim 7 or 8.
A positive electrode;
a negative electrode;
an electrolyte.
Wherein an electrolyte is interposed between the positive electrode and the negative electrode and comprises a sulfide solid electrolyte, an oxide solid electrolyte, a halide electrolyte, a nitride electrolyte, a polymer electrolyte, an organic electrolytic solution, or a combination thereof.
The application has the following advantages and beneficial effects:
1. the halide solid electrolyte material provided by the application has a metastable phase structure with high disorder degree and high internal energy and fast ion conduction capability, and the structure can realize an ultrafast ion conduction function not only comprising Li ions but also comprising Na, K, cu, ag, mg ions. The ion conduction rate is increased several times to more than a few orders of magnitude compared to the lower disorder structural material (fig. 1).
2. The halide solid electrolyte material provided by the application has the advantages that the metastable phase structure can stabilize a plurality of elements with larger structural difference through the effects of high confusion and high internal energy, so that the selection of ions in the development of the electrolyte material is not limited by the requirements of similar ion radius and coordination number. Not only expands the selection range of cations, but also reduces the cost of electrolyte materials by using cheap metal elements; but also can inhibit the phase separation caused by the instability of the crystal structure due to large cation difference. Thus realizing the development, preparation and application of the halide electrolyte material with low cost and excellent performance.
3. The halide solid electrolyte material provided by the application has higher ion conduction rate under the non-Li carrier condition (such as Na, K, ag, cu ions), is the highest value of a metal halide system under the corresponding carrier system, and has universality and creativity of the metastable phase structure with high confusion and high internal energy in the aspect of improving the ion conduction of the metal halide solid electrolyte material.
Drawings
The accompanying drawings, which are included to provide a further understanding of embodiments of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the principles of the application. In the drawings:
FIG. 1 is a graph showing the comparison of the ionic conduction rates of examples 1-6 and comparative examples 1-2. Wherein FIG. 1a is a graph showing the comparison of the ion conduction rates at room temperature of the materials obtained in examples 1 to 6 and comparative examples 1 and 2; FIG. 1b is a graph of the temperature swing ion conduction rates of the materials obtained in examples 1-6 and comparative examples 1 and 2.
FIG. 2 is a scanning electron microscope and EDS scanning image of the halide electrolyte material obtained in example 2.
Fig. 3 is a graph of temperature swing ion conduction rate for the non-Li carrier halide electrolyte material having a metastable phase structure obtained in example 9.
FIG. 4 is an X-ray diffraction spectrum of four halide electrolytes provided in example 1 (Li-LaCeZrAlTa-Cl), example 2 (Li-LaCeZrHfTa-Cl), comparative example 1 (Li-La-Cl), and comparative example 2 (Li-LaZr-Cl).
FIG. 5 compares example 2 (Li-LaCeZrHfTa-Cl), example 3 (Li-LaCeZrHfTaAl-Cl), comparative example 2 (Li-LaZr-Cl), structural sample (LaCl) 3 ) Structure sample (CeCl) 3 ) Raman spectra of 5 samples.
FIG. 6 is a graph showing the comparison of example 2 (Li-LaCeZrHfTa-Cl), example 10 (Li-LaCeZrHfTa-OCl), example 9 (Na-LaCeZrHfTa-Cl), example 9 (K-LaCeZrHfTa-Cl), example 9 (Cu-LaCeZrHfTa-Cl), example 9 (Ag-LaCeZrHfTa-Cl), and standard (LaCl) 3 ) Raman spectra of seven samples.
Fig. 7 is a graph showing the performance of the all-solid-state LiIn-NMC811 secondary battery obtained in application example 1.
Fig. 8 is a second cycle charge-discharge curve of all solid-state LiIn-NMC811 batteries obtained in application example 2 and application example 3.
Detailed Description
For the purpose of making apparent the objects, technical solutions and advantages of the present application, the present application will be further described in detail with reference to the following examples and the accompanying drawings, wherein the exemplary embodiments of the present application and the descriptions thereof are for illustrating the present application only and are not to be construed as limiting the present application.
Example 1
The embodiment provides a halide solid electrolyte material Li-LaCeZrAlTa-Cl with a metastable phase structure.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 And CeCl 3 (molar ratio 1:1), the halide containing 3M 2 ions with large structural difference from M1 is ZrCl 4 、TaCl 5 And AlCl 3 (molar ratio 1:1:1).
The preparation method comprises the following steps: 1.59 g LiCl and 1.23 g LaCl were weighed into a glove box 3 1.23 g CeCl 3 1.79 g of TaCl 5 1.16 g ZrCl 4 0.67 g AlCl 3 The materials are placed in a 200ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 25:1. Vacuum sealing the ball milling tank in a glove box, transferring into a ball mill, setting rotation speed at 500rpm, and ball milling for 10 hr to obtain a halide solid electrolyte material with metastable phase structure, denoted as Li-LaCeZrAlTa-Cl (Table 1,1.5LiCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 Sample 3).
Further, the addition amount of LiCl is regulated, and the regulation of the ion conduction rate at room temperature is realized through the regulation and control of the carrier concentration. The addition of LiCl was changed from 1.59 g to 0.398 g (sample 1), 0.796 g (sample 2), 1.592 g (sample 4) as described above, and the following samples were obtained, respectively, and were counted in table 1:0.5LiCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 、LiCl-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 、2LiCl-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 ；
Further, adjusting the M1 element component to be only La, adjusting the M2 element component content, keeping other conditions consistent, and obtaining the sample 5,2LiCl- (LaCl) 3 ·2ZrCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 。
Example 2
The embodiment provides a halide solid electrolyte material Li-LaCeZrHfTa-Cl with a metastable phase structure.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 And CeCl 3 (molar ratio 1:1), the halide containing 3M 2 ions with large structural difference from M1 is ZrCl 4 、TaCl 5 HfCl 4 (molar ratio 1:1:1).
The preparation method comprises the following steps: 1.59 g LiCl and 1.23 g LaCl were weighed into a glove box 3 1.23 g CeCl 3 1.79 g of TaCl 5 1.16 g ZrCl 4 3.2 g of HfCl 4 The materials are placed in a 200ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Vacuum sealing the ball milling tank in a glove box, transferring into a ball mill, setting rotation speed at 600rpm, and ball milling for 20h to obtain a halide solid electrolyte material with metastable phase structure, denoted as Li-LaCeZrHfTa-C (Table 1,1.5LiCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 Sample 7).
Further, the addition amount of LiCl is regulated, and the regulation of the ion conduction rate at room temperature is realized through the regulation and control of the carrier concentration. The addition of LiCl was changed from 1.59 g to 0.796 g (sample 6), 1.592 g (sample 8), 1.99 g (sample 9) as described above, and the following samples were obtained, respectively, and were counted in table 1: liCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 、2LiCl-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 、2.5LiCl-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2
Example 3
The embodiment provides a halide solid electrolyte material Li-LaCeZrHfAlTa-Cl with a metastable phase structure.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 And CeCl 3 (molar ratio 1:1), the halide containing 4M 2 ions with large structural difference from M1 is ZrCl 4 、TaCl 5 、AlCl 3 HfCl 4 (molar ratio 1:1:1:1).
The preparation method comprises the following steps: 1.91 g LiCl and 1.23 g LaCl were weighed into a glove box 3 1.23 g CeCl 3 1.79 g of TaCl 5 1.16 g ZrCl 4 3.2 g of HfCl 4 0.67 g AlCl 3 The materials are placed in a 200ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Vacuum sealing the ball milling tank in a glove box, transferring into a ball mill, setting the rotation speed to 400rpm, and ball milling for 12h to obtain a halide solid electrolyte material with metastable phase structure, which is denoted as Li-LaCeZrHfAlTa-Cl (Table 1,1.5LiCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·AlCl 3 ·TaCl 5 ) 0.167 Sample 13).
Example 4
The embodiment provides a halide solid electrolyte material Li-LaAlZrHfTa-Cl with a metastable phase structure.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 The halide containing 4M 2 ions with large structural difference from M1 is ZrCl 4 、AlCl 3 、TaCl 5 、HfCl 4 (molar ratio 1:1:1:1).
The preparation method comprises the following steps: 1.59 g LiCl and 1.23 g LaCl were weighed into a glove box 3 1.16 g ZrCl 4 0.67 g AlCl 3 1.79 g of TaCl 5 3.2 g of HfCl 4 The materials are placed in a 200ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Vacuum sealing the ball milling tank in a glove box, transferring to a ball mill, setting the rotation speed to 400rpm, and ball milling for 12h to obtain a halide solid electrolyte material with metastable phase structure, which is marked as Li-LaCeSmZrAl-Cl (sample 10,1.5LiCl- (LaCl) 3 ·AlCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 )。
Further, the M1 element was replaced with Ce, in accordance with the procedure described above, 1.23 g LaCl 3 Replaced by 1.23 g CeCl 3 Obtaining the sample 11,1.5LiCl- (CeCl) 3 ·AlCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2
Example 5
The embodiment provides a halide solid electrolyte material Li-LaCeHfAlTa-Cl with a metastable phase structure.
The same experimental procedure as in example 4 was used, with the difference that: 1.23 g LaCl was used as the starting material 3 1.23 g CeCl 3 0.67 g AlCl 3 1.79 g of TaCl 5 3.2 g of HfCl 4 A halide solid electrolyte material with a metastable phase structure was obtained, designated Li-LaCeHfAlTa-Cl (sample 12,1.5LiCl- (LaCl) 3 ·CeCl 3 ·HfCl 4 ·AlCl 3 ·TaCl 5 ) 0.2 )。
Example 6
The embodiment provides a halide solid electrolyte material Li-LaCeZrHfNb-Cl with a metastable phase structure.
The same experimental procedure as in example 2 was used, with the difference that: with 2.70 g NbCl 5 No TaCl is added 5 A halide solid electrolyte material with a metastable phase structure was obtained and designated as Li-laccezrhfnb-Cl (table 1, sample 14).
Example 7
The embodiment provides a halide solid electrolyte material Li-LaCeZrAlFTa-Cl with a metastable phase structure.
The same experimental procedure as in example 1 was used, with the difference that: with 0.16 g AlF 3 No AlCl is added 3 A halide solid electrolyte material with a metastable phase structure is obtained and is marked as Li-LaCeZrAlFTa-Cl.
Example 8
The embodiment provides a halide solid electrolyte material Li-LaCeZrAlBrTa-Cl with a metastable phase structure.
The same experimental procedure as in example 1 was used, with the difference that: with 0.53 g AlBr 3 No AlCl is added 3 A halide solid electrolyte material with a metastable phase structure is obtained and is marked as Li-LaCeZrAlBrTa-Cl.
Example 9
The embodiment provides a halide solid electrolyte material with a metastable phase structure, which is Na-LaCeZrHfTa-Cl, ag-LaCeZrHfTa-Cl or Cu-LaCeZrHfTa-C.
The preparation method comprises the following steps: the halide containing carrier ion is one of NaCl, agCl or CuCl, and the halide containing M1 cheap light rare earth element ion is LaCl 3 And CeCl 3 (molar ratio 1:1), the halide containing 3M 2 ions with large structural difference from M1 is ZrCl 4 、TaCl 5 HfCl 4 Preparation method of (molar ratio of 1:1:1)
The preparation method comprises the following steps: the same as in example 2, except that: the carrier is changed from Li to Na or K or Cu or Ag. In the case of the other metal halides, liCl was not added, instead 2.62 g NaCl or 3.35 g KCl or 6.45 g AgCl or 4.45 g CuCl were added. The resulting materials were designated as Na-LaCeZrHfTa-Cl (Table 1, sample 17), ag-LaCeZrHfTa-Cl (Table 1, sample 20), cu-LaCeZrHfTa-Cl (Table 1, sample 21), respectively.
Further, the carrier concentration is adjusted, the components and the content of M2 element are regulated, and other conditions are kept the same, thus obtaining 1.5NaCl- (2 LaCl) 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 (Table 1, sample 18) and 1.0NaCl- (LaCl) 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·AlCl 3 ) 0.2 (Table)1, sample 19) sample.
Example 9
The embodiment provides a halide solid electrolyte material Li-LaCeZrHfTa-OCl with a metastable phase structure.
The preparation method comprises the following steps: halide containing carrier ion is Li 2 O, the low-cost light rare earth element ion halide containing M1 is LaCl 3 And CeCl 3 (molar ratio 1:1), the halide containing 3M 2 ions with large structural difference from M1 is ZrCl 4 、TaCl 5 HfCl 4 (molar ratio 1:1:1).
The preparation method comprises the following steps: weigh 0.67 grams of Li in a glove box 2 O, 1.23 g LaCl 3 1.23 g CeCl 3 1.79 g of TaCl 5 1.16 g ZrCl 4 3.2 g of HfCl 4 The materials are placed in a 200ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Vacuum sealing the ball milling tank in a glove box, transferring into a ball mill, setting the rotating speed to 600rpm, and ball milling for 20h to obtain a halide solid electrolyte material with a metastable phase structure, which is denoted as Li-LaCeZrHfTa-OCl (Table 1, sample 15,0.75 Li) 2 O-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 )。
Further, li is reduced 2 The addition amount of O is 0.335 g, other conditions are kept consistent, and 0.375Li is obtained 2 O-(LaCl 3 ·CeCl 3 ·ZrCl 4 ·HfCl 4 ·TaCl 5 ) 0.2 (Table 1, sample 16).
Comparative example 1
The present case provides a halide electrolyte material, li-La-Cl.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 And does not contain M2 ions which are greatly different from M1 in structure.
The preparation method comprises the following steps: 1.06 g LiCl and 1.23 g LaCl were weighed into a glove box 3 The materials are placed in a 100ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. The ball-milling pot was vacuum-sealed in a glove box, and then transferred into a ball mill, and ball-milled for 12 hours at a rotation speed of 500rpm, to obtain a halide electrolyte material, which was designated as Li-La-Cl (Table 1, comparative example sample 1).
Further, the 1.23 g LaCl 3 The material was changed to 1.23 g CeCl3 to give comparative sample 2; 1.23 g LaCl 3 The material can be changed into 0.615 g CeCl3 and 0.615 g LaCl 3 Comparative sample 3 was obtained.
Comparative example 2
The present case provides halide electrolyte materials Li-LaZr-Cl, li-LaHf-Cl, li-LaAl-Cl, li-LaTa-Cl.
The preparation method comprises the following steps: the halide containing carrier ions is LiCl, and the halide containing M1 cheap light rare earth element ions is LaCl 3 Only 1M2 ion with a large structural difference from M1 is contained.
The preparation method comprises the following steps: 1.06 g LiCl and 1.23 g LaCl were weighed into a glove box 3 Material, 1.79 g of TaCl are weighed out 5 Or 1.16 g ZrCl 4 Or 3.2 grams of HfC l4 Or 0.67 g AlCl 3 The material was placed in a 100ml zirconia ball mill pot and zirconia balls of various sizes were added at a ball to material ratio of 35:1. The ball milling pot was vacuum sealed in a glove box, and then transferred to a ball mill, and the ball milling was performed for 12 hours at a rotational speed of 500rpm, to obtain a halide electrolyte material, which was designated as Li-LaZr-Cl (comparative example sample 5), li-LaHf-Cl (comparative example sample 8), li-LaAl-Cl (comparative example sample 7), li-LaTa-Cl (comparative example sample 6), respectively.
Further, la and Ce are adopted as M1 element, and 1.23 g of LaCl is adopted 3 The material can be changed into 0.615 g CeCl3 and 0.615 g LaCl 3 Comparative sample 4 was obtained.
Comparative example 3
The present case provides the halide electrolyte material NaCl- (LaCl) 3 ·ZrCl 4 ) 0.5 。
In a glove box, the molar ratio is 2:1:1 weighing LiCl, laCl 3 And ZrCl 4 The materials are placed in a 100ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Ball milling in glove boxVacuum sealing, transferring into ball mill, setting rotation speed at 500rpm, ball milling for 20 hr to obtain halide electrolyte material, named NaCl- (LaCl) 3 ·ZrCl 4 ) 0.5 (comparative sample 9).
Comparative example 4
The present case provides a halide electrolyte material AgCl-LaCl 3 。
In a glove box, the molar ratio is 1:1 weighing AgCl and LaCl 3 The materials are placed in a 100ml zirconia ball milling tank, zirconia balls with various sizes are added, and the ball-to-material ratio is 35:1. Vacuum sealing the ball milling tank in a glove box, transferring into a ball mill, setting the rotating speed to 500rpm, and ball milling for 20h to obtain a halide electrolyte material which is named AgCl-LaCl 3 (comparative sample 10).
Application example 1
The halide solid electrolyte Li-LaCeZrHfTa-Cl material with metastable phase structure obtained in example 2 was in all solid Liin-LiNi 0.8 Mn 0.1 Co 0.1 O 2 Use in (ilin-NMC 811) battery; the specific operation is as follows:
adopting unmodified NMC811 as a positive electrode material; the positive electrode material is as follows: the halide solid electrolyte material with the metastable phase structure obtained in example 2 was mixed in a ratio of 70:30 (mass ratio), the mixing mode was manually ground for 5min, the mixing process was performed in a glove box, and the obtained sample was the secondary battery anode powder.
The thin indium sheet is taken as a cathode, and the electrolyte is the halide solid electrolyte material with metastable phase structure obtained in the embodiment 2; 150mg of the solid electrolyte material of the halide having a metastable phase structure obtained in example 2 was put into a container having a cross-sectional area of 0.785cm 2 In the die battery liner, tabletting is carried out at the pressure of 100MPa to obtain the electrolyte layer.
Then, adding 10mg of positive electrode powder at one end of the obtained halide solid electrolyte layer with a metastable phase structure, uniformly paving, performing second tabletting at 350MPa, and laminating the positive electrode layer and the electrolyte layer together; after the pressing is finished, put in 5 at the other end0mg Li 6 PS 5 Cl is used as a barrier layer, and tabletting is carried out under the pressure of 100MPa to obtain a multi-layer tablet containing a negative electrode barrier layer, and then Li is used as a barrier layer 6 PS 5 Adding an indium sheet on one side of the Cl barrier layer to serve as a negative electrode layer, and tabletting for the third time by adopting the pressure of 50 MPa; after the whole process is finished, the inner container is put into a die battery, and the screw is tightly pressed and screwed for sealing. After sealing, an all-solid Liin-NMC811 secondary battery can be obtained.
Characterization of scanning electron microscopy, X-ray diffraction (XRD), ion conduction rate, etc. was performed on the obtained samples. Application verification was then performed in all-solid-state batteries using representative halide solid-state electrolyte materials with metastable phase structures.
Application example 2
All-solid Liin-LiNi was assembled by the method described in application example 1 0.8 Mn 0.1 Co 0.1 O 2 (ilin-NMC 811) cell, differing in that: the halide solid electrolyte used was Li-LaCeZrAlTa-Cl synthesized in example 1, which was exposed to air at a dew point of-50 ℃ (relative humidity of 0.1%) for 60min. The electrolyte has a metastable phase structure and contains Al ions for improving air stability.
Application example 3
All-solid Liin-LiNi was assembled by the method described in application example 1 0.8 Mn 0.1 Co 0.1 O 2 (ilin-NMC 811) cell, differing in that: the halide solid electrolyte used was Li synthesized in comparative example 3 2 ZrCl 6 The exposure was carried out for 60min in air with a dew point of-50 ℃ (relative humidity of 0.1%). The electrolyte is a traditional ternary halide electrolyte and does not contain Al ions for improving air stability.
FIG. 1a is a graph showing the comparison of the ion conduction rates at room temperature for the materials obtained in examples 1 to 6 and comparative examples 1 and 2, and FIG. 1b is a graph showing the temperature-changing ion conduction rates for the materials obtained in examples 1 to 6 and comparative examples 1 and 2. It can be seen from the figure that the Li-La-Cl or Li-Ce-Cl (La or Ce point in FIG. 1) halides obtained from the structure of A-M1-X exhibit a lower ionic conduction rate, below 10 -6 S/cm. Comparative example 2, after further modification and ratio optimization with modified ions, the solution was isolatedThe sub-conduction energy is improved but is lower than 3×10 -4 S/cm. In examples 1-6, the ionic conductivity of all the halide electrolyte materials with metastable phase structure can be effectively improved by more than one order of magnitude, and the ionic conductivity of the halide solid electrolyte materials at room temperature can be realized by optimizing the proportion>10 -3 S/cm, and potential application value is shown.
Table 1 shows the room temperature ion conduction rates of the materials obtained in the examples and their extensions and their comparative samples.
FIG. 2 is a scanning electron microscope and EDS facial scan of the halide electrolyte material obtained in example 2. The graph shows that the material is composed of hundred-nanometer-scale small particles, is formed by mixing and arranging a plurality of metal elements, and has no obvious phenomenon of agglomeration of a certain metal element. Wherein the crystalline phase is rich in La and Ce elements, and all metal elements in the amorphous phase are distributed.
FIG. 3 is a graph showing the temperature-changing ion conduction rate of the non-Li carrier halide solid electrolyte material having a metastable phase structure obtained in example 9, which is Na-LaCeZrHfTa-Cl, K-LaCeZrHfTa-Cl, ag-LaCeZrHfTa-Cl, cu-LaCeZrHfTa-Cl, respectively. These materials all exhibit a high ionic conduction rate, which is the highest value of the metal halide system under the corresponding carrier system, and exhibit the universality and creativity of the metastable phase structure with high disorder and high internal energy in the aspect of improving the ionic conduction of the halide solid electrolyte material; in particular, ag-LaCeZrHfTa-Cl, cu-LaCeZrHfTa-Cl exhibit excellent ion conduction rates.
FIG. 4 compares the X-ray diffraction spectra of four halide solid electrolytes of example 1 (Li-LaCeZrAlTa-Cl), example 2 (Li-LaCeZrHfTa-Cl), comparative example 1 (Li-La-Cl), and comparative example 2 (Li-LaZr-Cl). The results show that the above four halide solid electrolytes with metastable phase structures have similar X-ray diffraction patterns. The metastable phase structure with high confusion and high internal energy can tolerate different cations, inhibit crystal phase structure collapse caused by modified ions with large doping structure difference, and improve structural stability.
FIG. 5 compares example 2 (Li-LaCeZrHfTa-Cl), example 3 (Li-LaCeZrHfTaAl-Cl), comparative example 2 (Li-LaZr-Cl), structural sample (LaCl) 3 ) Structure sample (CeCl) 3 ) Raman spectra of 5 halide solid state electrolytes. Sample at retention of LaCl 3 Outside the characteristic vibration peak of (2) at 250-400 cm -1 Exhibits a broader vibration peak in the range, and additionally LaCl 3 The characteristic vibration peaks of (2) also exhibited a large spread, indicating that the material obtained in the examples had a highly chaotic structure. Peak 1 at 210+ -5 cm -1 Position, peak 2 at 340.+ -.5 cm -1 A location; the peak intensity ratio a (half-width times peak height) of the peak 1 to the peak 2 obtained in examples 2 and 3 was less than 0.5, indicating that the obtained sample had a highly disordered structure, in contrast, comparative example 2 (Li-LaZr-Cl), structure sample (LaCl 3 ) Structure sample (CeCl) 3 ) Exhibit a high peak-to-peak intensity ratio a, a of peak 1 to peak 2>10。
FIG. 6 is a graph showing the comparison of example 2 (Li-LaCeZrHfTa-Cl), example 10 (Li-LaCeZrHfTa-OCl), example 9 (Na-LaCeZrHfTa-Cl), example 9 (K-LaCeZrHfTa-Cl), example 9 (Cu-LaCeZrHfTa-Cl), example 9 (Ag-LaCeZrHfTa-Cl), and standard (LaCl) 3 ) Raman spectra of seven halide solid state electrolytes. Sample at retention of LaCl 3 Outside the characteristic vibration peak of (2) at 250-400 cm -1 Exhibits a broader vibration peak in the range, and additionally LaCl 3 The characteristic vibration peaks of (2) also exhibited a large spread, indicating that the material obtained in the examples had a highly chaotic structure. Peak 1 at 210+ -5 cm -1 Position, peak 2 at 340.+ -.5 cm -1 A location; the peak intensity ratio a (half-width times peak height) of the peak 1 to the peak 2 obtained in example 2 (Li-LaCeZrHfTa-Cl), example 10 (Li-LaCeZrHfTa-OCl), example 9 (Na-LaCeZrHfTa-Cl), example 9 (K-LaCeZrHfTa-Cl), example 9 (Cu-LaCeZrHfTa-Cl), and example 9 (Ag-LaCeZrHfTa-Cl) was much smaller than 0.5, further indicating that the resulting samples have a highly chaotic structure.
FIG. 7 is a graph showing the performance of an all-solid Liin-NMC811 battery obtained in application example 1, in which the halide solid electrolyte material with metastable phase structure obtained in example 2 exhibits good rate performance and low polarization potential in an all-solid battery with reversible cycle capacity of 180mAh cm at 1C -2 Can still reach 90mAh cm under the condition of 5C -2 Is a reversible capacity of (a).
Fig. 8 compares the second cycle charge and discharge curves of all solid-state LiIn-NMC811 batteries obtained in application example 2 and application example 3. The results showed that the battery in application example 2 had a higher specific discharge capacity. This is because the ternary halide solid electrolyte Li in application example 3 during air exposure 2 ZrCl 6 The ionic conductivity is obviously reduced due to the fact that the air stability is poor and hydrolysis occurs; in contrast, the halide solid electrolyte Li-LaCeZrAlTa-Cl material with a metastable phase structure has better air stability, maintains high ion conductivity, and thus shows higher discharge capacity in an all-solid-state battery.
The foregoing description of the embodiments has been provided for the purpose of illustrating the general principles of the application, and is not meant to limit the scope of the application, but to limit the application to the particular embodiments, and any modifications, equivalents, improvements, etc. that fall within the spirit and principles of the application are intended to be included within the scope of the application.
Claims (10)
1. A halide solid electrolyte material having a metastable phase structure, characterized in that,
electrolyte material a-M1M2-X, wherein:
x is halogen, including one or more than two of F, cl, br, I;
a is a carrier and comprises one or more than two of Li, na, K, cu, ag, mg ions;
m1 is a rare earth element, and comprises one or more than two of La, ce and Sm;
m2 is doped metal, satisfying: the coordination number difference between M1 and M2 is more than or equal to 1.15; the difference of the ionic radius of M1 and M2 is more than or equal to 1.25 according to the calculation of the crystallographic ionic radius.
2. A halide solid state electrolyte material having a metastable phase structure as claimed in claim 1, wherein M2 comprises a combination of two or more of Ta, zr, hf, al, nb, ga.
3. A halide solid electrolyte material having a metastable phase structure as claimed in claim 1,
a is a carrier and is one or the combination of more than two of Na, K, cu, ag, mg ions; the content of the carrier substance accounts for 20% -75% of the content of all cations.
4. The halide solid electrolyte material of claim 1, further comprising modifying/doping ions: o, N, P, S, B, H, C, in, yb, Y, ho, zn, or a combination of two or more thereof.
5. A halide solid electrolyte material having a metastable phase structure as claimed in claim 1,
metastable phase structure in X-ray diffraction measurements using copper kα rays:
a diffraction peak at a position of 2θ=13.7° ±0.2°;
and/or, the optical fiber has double diffraction peaks at the positions of 2 theta = 23.7 degrees +/-0.15 degrees to 2 theta = 24.8 degrees +/-0.15 degrees, and the peak intensity ratio is 0.2 to 5;
and/or, having diffraction peaks at positions 2θ=31.7° ±0.15°,2θ=34.7° ±0.15°,2θ=42.6° ±0.15°, wherein a plurality of diffraction peaks are present in the vicinity of the position 2θ=42.0° ±1.0°;
and/or metastable phase structure in use of 512cm -1 In Raman spectrometer measurement of laser：
Sample at retention of LaCl 3 Outside the characteristic vibration peak of (2), at 250cm -1 ～400cm -1 Exhibiting a vibration peak in the range; wherein, contain: peak 1 is 210+ -10 cm -1 Position, peak 2 at 340.+ -.10 cm -1 A location; the peak intensity ratio a of the peak 1 to the peak 2 is less than or equal to 5.
6. A halide solid electrolyte material having a metastable phase structure according to claim 1, comprising an amorphous phase in which carriers, M1 and a plurality of M2 metal cation elements are mixed;
alternatively, a crystalline phase comprising a portion of the constituent elements in the amorphous phase is also included.
7. A method for preparing a halide solid electrolyte material having a metastable phase structure, comprising the steps of: one or more of halide, oxide or oxyhalide compounds of metal cations including carrier ions, M1 ions and M2 ions are mixed and ball-milled by a ball-milling synthesis means.
8. Use of a halide solid state electrolyte material having a metastable phase structure, characterized by being applied in a solid state battery; the halide solid electrolyte material is a halide solid electrolyte material having a metastable phase structure according to any one of claims 1 to 6, or a material obtained by the production method of a halide solid electrolyte material having a metastable phase structure according to claim 7 or 8.
9. The use of a halide solid electrolyte material having a metastable phase structure according to claim 8, as electrolyte material or additive to positive and negative electrode materials and electrolyte material, as solid electrolyte, solid electrolyte stabilizer, positive and negative electrode ion conducting additive or electrode-electrolyte interface modifier.
10. A battery, comprising:
a halide solid electrolyte material having a polycation mixed structure, which is a halide solid electrolyte material having a metastable phase structure according to any one of claims 1 to 6, or a material obtained by a process for producing a halide solid electrolyte material having a metastable phase structure according to claim 7 or 8.
A positive electrode;
a negative electrode;
an electrolyte.
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