WO2020220697A1 - 锂二次电池固态电解质材料、电极及电池 - Google Patents

锂二次电池固态电解质材料、电极及电池 Download PDF

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WO2020220697A1
WO2020220697A1 PCT/CN2019/126451 CN2019126451W WO2020220697A1 WO 2020220697 A1 WO2020220697 A1 WO 2020220697A1 CN 2019126451 W CN2019126451 W CN 2019126451W WO 2020220697 A1 WO2020220697 A1 WO 2020220697A1
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solid electrolyte
electrolyte material
phase
electrode
secondary battery
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PCT/CN2019/126451
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English (en)
French (fr)
Inventor
孙学良
李晓娜
梁剑文
王长虹
黄欢
卢世刚
张立
赵尚骞
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国联汽车动力电池研究院有限责任公司
西安大略大学
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Priority claimed from CN201910354433.XA external-priority patent/CN110137561A/zh
Priority claimed from CN201910381153.8A external-priority patent/CN111916820B/zh
Priority claimed from CN201910843405.4A external-priority patent/CN112467074A/zh
Priority claimed from CN201910843347.5A external-priority patent/CN112467196A/zh
Application filed by 国联汽车动力电池研究院有限责任公司, 西安大略大学 filed Critical 国联汽车动力电池研究院有限责任公司
Priority to EP24167706.1A priority Critical patent/EP4371942A2/en
Priority to EP19926754.3A priority patent/EP3965199A4/en
Priority to JP2021564642A priority patent/JP7390692B2/ja
Priority to US17/607,849 priority patent/US20220216507A1/en
Publication of WO2020220697A1 publication Critical patent/WO2020220697A1/zh

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    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Definitions

  • the invention relates to a lithium secondary battery additive, a battery and an electrode, in particular to an additive material capable of improving the rapid transmission of ions of a lithium secondary battery electrode, a preparation method and application thereof, a solid electrolyte material for a secondary battery, and a preparation method and application thereof. And an electrode, an electrolyte thin layer and a preparation method thereof.
  • lithium secondary batteries are an ideal battery system.
  • the electrochemical performance of lithium secondary batteries is still limited by the transfer rate of ions and electrons in the electrode layer.
  • the electron transmission channel of the electrode is mainly provided by adding conductive carbon and other electronic highly conductive materials.
  • the method of providing ion transport channels for electrodes is different between organic phase lithium secondary batteries and all-solid-state lithium secondary batteries. Since the organic electrolyte has high permeability and wetting ability, in the electrode preparation process, by preserving pores in the electrode layer, the infiltration of the electrolyte in the electrode layer is realized to realize the transmission of ions in the electrode layer.
  • the present invention first provides a lithium secondary battery additive, which has high ionic conductivity and air stability, can improve the rapid transmission of electrode ions, increase the electrode load and thickness, and is compatible with existing lithium secondary battery electrode materials It is expected to solve the problems of slower ion transmission of electrode materials in lithium secondary batteries, low electrode material load, and difficulty in further increasing the electrode thickness, so that it is expected to realize the preparation of electrode pads with high energy density and low electrode polarization. Improve the energy density of lithium secondary batteries.
  • the lithium secondary battery additive has higher room temperature ion conductivity, stable air, and simple preparation method.
  • the present invention provides a lithium secondary battery additive represented by the following formula:
  • M is selected from B, Al, Ga, In, Y, Sc, Sb, Bi, Nb, Ta, Ti, Zr, V, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Cu
  • X is selected from F, Cl , Br, one or more of I; 0.2 ⁇ b ⁇ 6; 0.1 ⁇ a ⁇ 3; 1 ⁇ c ⁇ 9.
  • b can be selected from 0.2, 0.5, 1, 2, 3, 4, 5 or 6, and more preferably, 1 ⁇ b ⁇ 3.
  • a may be selected from 0.1, 0.2, 0.5, 1, 1.5, 2, 2.5 or 3, and more preferably, 0.2 ⁇ a ⁇ 1.
  • c may be selected from 1, 2, 3, 4, 5, 6, 7, 8 or 9, more preferably, 3 ⁇ c ⁇ 6.
  • the lithium secondary battery additives are as follows:
  • Li 3 Y 1-d In d Cl 6 (glass-ceramic phase); wherein 0 ⁇ d ⁇ 1; further, d is selected from 0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8, 0.9 or 1.0.
  • the lithium secondary battery additive of the present invention may be a glass phase, a glass-ceramic phase or a crystalline phase.
  • the lithium secondary battery additives are as follows:
  • Li 3 InCl 6 (crystalline phase), Li 3 NbCl 8 (glass phase), Li 3 YCl 6 (glass-ceramic phase).
  • lithium secondary battery additives of the present invention can be prepared according to conventional techniques in the field.
  • it can be prepared by mixing the required raw materials (or precursors) according to the proportions and then grinding; or further adopting organic solvent co-solution recrystallization method, heating eutectic method, insoluble hydrocarbon organic solvents to make the raw material particles contact. Into the corresponding phase of the compound.
  • the raw materials (or precursors) for preparing the lithium secondary battery additives of the present invention include LiX and MX y precursors, wherein the definitions of M and X are the same as above; 1 ⁇ y ⁇ 6, preferably, 2 ⁇ y ⁇ 5.
  • y can be selected from 1, 2, 3, 4, 5, or 6.
  • the mixing can be carried out in a ball or bead manner, or in a non-spherical or bead manner. It may be mixed in an organic solvent, or may be mixed without using an organic solvent.
  • the organic solvent may be a polar solvent or a non-polar solvent.
  • the solvent can dissolve, partially dissolve and insoluble the aforementioned LiX and MX y precursors.
  • non-polar solvents include hydrocarbon solvents and ether solvents.
  • hydrocarbon solvent include aliphatic hydrocarbon solvents and aromatic hydrocarbon solvents. Preferably it is an aliphatic hydrocarbon solvent, More preferably, it is hexane.
  • the ether solvent include cyclic ester solvents and chain ester solvents, and cyclic ester solvents are preferred, and tetrahydrofuran is more preferred.
  • NH 4 Cl, I 2 , LiI, S and other materials can be used as cosolvents and fluxes during the mixing process of required raw materials (or precursors).
  • the ligand of the complex is used.
  • the advantage is that the reaction temperature can be lowered, the formation of complex intermediates, etc. are conducive to the acquisition of products.
  • the obtained glass phase or glass-ceramic phase intermediate product can be converted into a glass-ceramic phase or crystalline phase by a heating annealing method.
  • the heating annealing temperature is 100-600°C, preferably 150-350°C.
  • the heating annealing time is usually 10 minutes to 24 hours, preferably 1 to 10 hours. Heating annealing can be performed in an atmosphere such as air, nitrogen, argon, or the like, or in a vacuum atmosphere.
  • volatile materials such as NH 4 Cl, I 2 , LiI, S, P, and ferrocene can also be added during the heating and annealing process to control the phase and morphology. Its advantage lies in lowering the annealing temperature and at the same time helping to improve the ion conductivity of the material.
  • the invention also includes the lithium secondary battery additives prepared by the above method.
  • the present invention also includes the application of the above-mentioned lithium secondary battery additive as an electrode additive in a lithium secondary battery, or an application in the preparation of a lithium secondary battery.
  • the use of the additive of the present invention can improve the ion transmission speed of the electrode and is compatible with existing lithium secondary battery electrode materials.
  • the present invention also provides a lithium secondary battery, wherein at least one of the positive electrode layer, the electrolyte layer and the negative electrode layer of the battery contains one or more of the foregoing lithium secondary battery additives.
  • the lithium secondary battery includes liquid phase lithium secondary batteries, semi-solid and all-solid lithium secondary batteries.
  • the lithium secondary battery of the present invention can be prepared according to conventional methods in the field.
  • the lithium secondary battery additive provided by the present invention can be used as an additive material for improving the rapid transmission of electrode ions.
  • the material can be used not only in organic phase lithium secondary batteries, but also in all-solid or semi-solid lithium secondary batteries.
  • the lithium secondary battery additive provided by the present invention has the following advantages:
  • the electrode additive materials proposed in the present invention are stable under air conditions, and are compatible with the solvents used in the preparation of lithium secondary battery electrode plates such as NMP (nitrogen methyl pyrrolidone) and adhesives such as PVDF (polypolarized Difluoroethylene) does not undergo chemical reactions. Further, it is compatible with existing lithium secondary battery electrode materials such as sulfur, lithium sulfide, lithium cobalt oxide, lithium manganese oxide, lithium iron phosphate, lithium nickel manganese cobaltate, high-voltage phase lithium nickel manganese oxide, and lithium-rich phase manganese-based electrode materials And other chemical compatibility. It can be directly applied to the existing mature electrode preparation process.
  • NMP nitrogen methyl pyrrolidone
  • PVDF polypolarized Difluoroethylene
  • the electrode additive material proposed in the present invention has the characteristics of high ionic conductivity at room temperature. After being mixed with the active electrode material, it can improve the rapid conduction of lithium ions between the active electrode material and the electrolyte. Therefore, the addition of this material is beneficial to reduce the interface impedance between the active particles in the electrode sheet and between the active particles and the electrolyte, thereby improving the rate performance of the lithium secondary battery and the loading of the active material, and further helping to increase the lithium secondary battery.
  • the energy density of the secondary battery is beneficial to reduce the interface impedance between the active particles in the electrode sheet and between the active particles and the electrolyte, thereby improving the rate performance of the lithium secondary battery and the loading of the active material, and further helping to increase the lithium secondary battery.
  • the electrode additive material proposed by the present invention has a wide operating temperature and electrochemical inertness, with an electrochemical window of more than 6 volts, and will not decompose during battery charging and discharging. At the same time, the material has a simple preparation method and is easy to use in lithium secondary batteries.
  • All solid-state secondary batteries have higher safety than current commercial organic-phase secondary batteries. This is because the all-solid secondary battery uses non-flammable solid fast ion materials as the electrolyte.
  • the electrolyte uses non-flammable solid fast ion materials as the electrolyte.
  • the sulfide electrolyte includes Li 10 Ge 2 P 2 S 12 , Li 6 PS 5 Cl, Li 7 P 3 S 11 and Li 3 PS 4, etc.
  • the oxide electrolyte mainly includes Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 , Li 7 La 3 Zr 2 O 12 and so on.
  • the sulfide electrolyte is unstable in air and water, and is prone to generate toxic gases such as hydrogen sulfide. It needs to be operated in an environment where an inert gas is a protective atmosphere; the oxide electrolyte needs to be phased under high temperature conditions, and the phase temperature is 1000 Above °C, mass production is difficult.
  • the present invention also provides a secondary battery solid electrolyte material, which has high ionic conductivity (higher than 1mS cm -1 ), is stable in air and water, and is compatible with commercially used oxides such as LCO and NMC. Compatible with cathode materials. It is expected to solve the problems of complex process, time-consuming, energy-consuming, and high price in the mass preparation of solid electrolyte materials in all-solid secondary batteries. It can further solve the problems of chemical and electrochemical instability of solid electrolyte materials in all solid-state secondary batteries. So as to realize the commercial application value of all solid-state secondary batteries.
  • the present invention provides a solid electrolyte material for a secondary battery as shown in the following formula:
  • A is selected from one or more of Li, Na, K, and Cs;
  • X is selected from one or more of F, Cl, Br, and I; 0 ⁇ z ⁇ 0.33.
  • 0.1 ⁇ z ⁇ 0.25 for example, specifically, z can be selected from 0, 0.25, 0.2, 0.167, 0.143 or 0.1.
  • the solid electrolyte material is represented by any of the following formulas:
  • Li 1-3z In z Cl z is 0.25, 0.2, 0.167, 0.143 or 0.1;
  • the In may be partially or completely replaced by the following elements to form a new electrolyte material.
  • the replaceable elements are Al, Ga, Sc, Y, La, Ce, Pr, Nd, Pm One or more of, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Fe, Bi, Sb, Cr, Co, Zr, Zn, Cd, Mg.
  • the solid electrolyte material is represented by any of the following formulas: Li 3 In 0.8 Y 0.2 Cl 6 , or Li 2 In 0.1 Zn 0.9 Cl 4.1 , or LiGaCl 4 , or Li 6 FeCl 8 , or Li 3 YCl 6 , or Li 3 BiCl 6 .
  • the solid electrolyte material of the present invention may be a glass phase, a glass-ceramic phase or a crystalline phase.
  • the solid electrolyte material of the present invention includes a main crystalline phase, and the crystalline phase has a twisted rock salt phase structure.
  • the solid electrolyte material of the present invention may include a heterogeneous crystal phase, and the heterogeneous crystal phase and the main crystal phase have different crystal structure arrangements.
  • the solid electrolyte material of the present invention may include an amorphous phase.
  • the above solid electrolyte materials of the present invention can be prepared according to conventional techniques in the art.
  • the foregoing solid electrolyte material of the present invention is prepared by an aqueous phase method.
  • the raw materials (or precursors) used include but are not limited to AX, InX 3 and MX a ; wherein A and X have the same meaning as above; M is Al, Ga, Sc, Y, La, Ce, Pr, Nd, One or more of Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Fe, Bi, Sb, Cr, Co, Zr, Zn, Cd, Mg; 2 ⁇ a ⁇ 4.
  • the raw materials AX, InX 3 and MX a can be expanded into their corresponding hydrates or solutions.
  • the raw materials AX, InX 3 and MX a can be expanded to free or react with precursors with equivalent ionic effects in the water phase, including but not limited to carbonate and bicarbonate.
  • HCl, NH 4 Cl, etc. can be appropriately added as a hydrolysis inhibitor or complexing agent during the preparation process.
  • the above-mentioned aqueous phase method specifically includes: dissolving the required raw materials or precursors in the water phase in a certain proportion, and the mass ratio of the required raw materials or precursors to the water phase is 1:0.5 to 1:15, preferably 1 :2 ⁇ 1:5.
  • the above-mentioned water phase method can dissolve the required raw materials or precursors in the water phase at room temperature, and after all the components are dissolved, the solid electrolyte material can be obtained by drying.
  • the drying temperature is usually 60-100°C, and the drying can be carried out under vacuum or non-vacuum conditions. For example, drying can be carried out in an oven.
  • annealing treatment may be performed after drying, and the annealing temperature is 100-600°C, preferably 120-500°C. Its advantage is to improve the crystallinity of the material, which is beneficial to improve the stability and ion conductivity of the material.
  • the annealing is performed in an air atmosphere, and can also be performed in an inert gas atmosphere or a vacuum atmosphere.
  • the aqueous phase of the above preparation method can not only use deionized water, but also use an organic solvent or a mixed solvent of organic solvent/water for expansion.
  • the organic solvent in the above preparation method is an alcohol, such as ethanol.
  • the present invention also includes the solid electrolyte material prepared by the above method.
  • the solid electrolyte material of the present invention can be used not only as an additive for secondary batteries, but also as an electrolyte for secondary batteries.
  • the present invention also includes the application of the above solid electrolyte material in the preparation of secondary batteries.
  • the use of the solid electrolyte material of the present invention can improve the electrode ion transmission speed and is compatible with existing secondary battery electrode materials.
  • the present invention also provides a secondary battery, which includes a positive electrode (layer), a negative electrode (layer), and an electrolyte layer between the positive electrode (layer) and the negative electrode (layer); the positive electrode (layer), the negative electrode At least one of the (layer) and the electrolyte layer contains one or more of the above solid electrolyte materials.
  • the secondary battery in the present invention includes a lithium secondary battery and a sodium secondary battery.
  • the secondary battery of the present invention can be prepared according to conventional methods in the art.
  • the solid electrolyte material provided by the present invention is stable in air and water phases without decomposition; its ion conductivity can be higher than 1mS cm -1 ; it has a wide working temperature and electrochemical inertness, and its electrochemical window is more than 5 volts. It is stable to oxide positive electrodes, does not decompose during battery charging and discharging, and is easy to be used in secondary batteries.
  • the solid electrolyte material provided by the present invention has a low phase forming temperature, and can even form a phase after ball milling or drying in an aqueous phase at room temperature; the preparation method is simple and easy to prepare and apply in large quantities.
  • Halide electrolyte materials such as Li 3 YCl 6 , Li 3 InCl 6 and other materials are stable with high-voltage anodes, can be operated in a dry room, and the materials are soft, easy to mold and process, and are expected to be industrially applied.
  • the ion conductivity of halide electrolyte materials is generally low, and its ion conductivity needs to be further improved.
  • Li 3 InCl 6 electrolyte material was reported as early as 1992, and its room temperature ion conductivity is only 10 -5 S/cm (Zeitschrift für anorganische undwoven Chemie 1992, 613, 26-30.), which is still not satisfactory The need for lithium secondary batteries.
  • the present invention also provides a solid electrolyte material with high lithium ion conductivity.
  • the inventors of the present invention have found in practice that the lithium ion conductivity can be improved by adjusting the arrangement of atoms in the crystal structure, thereby obtaining an indium-based halide electrolyte material with an ion conductivity of >10 -3 S/cm (room temperature) .
  • the indium-based halide electrolyte Li 3b-3a In a Cl 3 material obtained by structural adjustment has higher ion conductivity.
  • the solid electrolyte material obtained by the present invention is compatible with commercially used oxide cathode materials such as LCO and NMC, and is stable to air.
  • the present invention can further solve the problems of solid electrolyte material chemistry and electrochemical instability in the all-solid secondary battery. So as to realize the commercial application value of all solid-state secondary batteries.
  • the present invention provides a solid electrolyte material, which has a composition shown by Li 3b-3a In a Cl 3 , where 0.2 ⁇ a ⁇ 0.8, 0.9 ⁇ b ⁇ 1.15; and also has a first crystal phase.
  • the atomic arrangement is similar to the twisted LiCl crystal structure
  • the arrangement of Cl ions is similar to the arrangement of Cl ions in the twisted LiCl crystal structure.
  • Li ions, vacancies, and indium ions are arranged in Li sites in the twisted LiCl crystal structure.
  • the occupying positions of the indium ion and the lithium ion are not in the same position.
  • the vacancy arrangement in the first crystal phase, has two types, one is co-located with indium ions, and the other is not co-located with any ions.
  • the X-ray intensity of the (001) plane in the crystal structure is set to I (001)
  • the X-ray intensity of the (131) plane in the crystal structure is set to Is I (131)
  • I (001) /I (131) > 0.6 is satisfied.
  • the X-ray intensity of the (001) plane in the crystal structure is set to I (001)
  • the X-ray intensity of the (110) plane in the crystal structure is set to Is I (110)
  • I (110) /I (001) ⁇ 0.85 is satisfied.
  • the heterogeneous crystal phase has a crystal structure different from the first crystal phase, and the heterogeneous crystal phase is between the first crystal phase.
  • the solid electrolyte material of the present invention also includes an amorphous phase.
  • the amorphous phase is interposed between the first crystal phase.
  • a in the solid electrolyte material, 0.3 ⁇ a ⁇ 0.7, 0.95 ⁇ b ⁇ 1.10; for example, specifically a may be 0.53, and b may be 1.03.
  • the solid electrolyte material of the present invention has the above-mentioned first crystal phase, it has a higher ion conductivity; especially when it further has the above-mentioned heterogeneous crystal phase and amorphous phase, it can also be used with commercial products such as LCO, NMC, etc. Oxide cathode materials are compatible and stable to air.
  • the solid electrolyte material of the present invention has an ion conductivity (room temperature) of >10 -3 S/cm.
  • the solid electrolyte material has an ionic conductivity of 0.7-2.5 mS/cm.
  • the solid electrolyte material has an ion conductivity of 1.0-2.0 mS/cm.
  • the solid electrolyte material has a composition shown as Li 1.5 In 0.53 Cl 3 , and after testing, the material has an ion conductivity of 2 mS/cm at room temperature.
  • the X-ray diffraction (measured using copper K ⁇ rays) of the solid electrolyte material is shown in Figure 24 below.
  • the solid electrolyte material of the present invention can be prepared by an aqueous phase method.
  • Raw materials used (or precursors) include lithium source and the indium source, wherein the lithium source comprises LiCl, Li 2 CO 3, LiHCO 3, LiOH , or lithium acetate; indium source comprises InCl 3, InCl 3 ⁇ 4H 2 O, In 2 O 3. InOCl.
  • HCl, NH 4 Cl, etc. can be appropriately added as a hydrolysis inhibitor or complexing agent.
  • the aqueous phase method specifically includes: dissolving the required raw materials or precursors in a certain ratio in the aqueous phase.
  • the required raw materials or precursors can be dissolved in the water phase at room temperature, and after all the components are dissolved, the solid electrolyte material can be obtained by drying.
  • the drying temperature is usually 60-100°C, for example 80°C, and drying can be performed under vacuum or non-vacuum conditions. For example, drying can be carried out in an oven.
  • the dried sample needs to be further removed of crystal water under vacuum conditions, and the dehydration temperature is 100-300°C, preferably 120-250°C.
  • an annealing treatment may be further performed after dehydration, and the annealing temperature is 300-600°C, preferably 350-550°C. Its advantage lies in improving the crystallinity of the material, which is conducive to improving the stability and ion conductivity of the material.
  • the annealing is performed in an air atmosphere, and can also be performed in an inert gas atmosphere or a vacuum atmosphere.
  • aqueous phase of the preparation method can not only use deionized water, but also use an organic solvent or a mixed solvent of organic solvent/water for expansion.
  • the organic solvent in the preparation method is an alcohol, such as ethanol.
  • the present invention also provides an all-solid lithium battery having a positive electrode active material layer, a negative electrode active material layer, and a solid electrolyte layer formed between the positive electrode active material layer and the negative electrode active material layer, wherein the positive electrode active material layer, At least one of the negative electrode active material layer and the solid electrolyte layer contains the solid electrolyte material described above.
  • an all-solid lithium battery with high output characteristics can be manufactured. Furthermore, the all-solid-state lithium battery also has higher chemical and electrochemical stability.
  • the solid electrolyte material provided by the present invention at least achieves the technical effect of high lithium ion conductivity, and further achieves the technical effect of chemical and electrochemical stability.
  • All solid-state secondary batteries have higher safety and higher energy density than current commercial liquid secondary batteries. This is because the all-solid secondary battery uses a non-flammable solid fast ion conductor material as the electrolyte.
  • the electrolyte uses a non-flammable solid fast ion conductor material as the electrolyte.
  • several solid electrolyte materials with ion conductance higher than 1mS cm -1 have been developed.
  • sulfide solid electrolytes represented by Li 10 Ge 2 P 2 S 12 , Li 6 PS 5 Cl, Li 7 P 3 S 11 and Li 3 PS 4 .
  • the sulfide electrolyte is extremely sensitive to air and water, and is prone to produce toxic gases such as hydrogen sulfide.
  • the electrochemical stability window of the sulfide electrolyte is narrow (1.7 ⁇ 2.8V), and the interface reaction occurs with oxide electrode materials (such as LiCoO 2 , NMC, Graphite, etc.), so the interface modification (surface coating of the electrode material) Sulfide-based all-solid-state batteries have become indispensable; in addition, due to the chemical instability of sulfide, it is easy to react with polar solvents, so the solvent and bonding can be selected in the electrode process such as slurry preparation and electrode coating.
  • the agent is very limited. Due to the above shortcomings, the capacity for mass production and application of sulfide-based all-solid-state batteries is very limited. Based on this, the present invention is further proposed.
  • the invention also provides an electrode (specifically an electrode based on a halide solid electrolyte material) and a preparation method thereof.
  • the invention also provides an electrolyte thin layer (specifically an electrolyte thin layer based on a halide solid electrolyte material) and a preparation method thereof.
  • the present invention also provides a battery containing the electrode or the thin electrolyte layer.
  • the invention uses solid electrolyte materials as ion conductive additives to prepare electrodes or electrolyte thin layers.
  • One of its significant advantages is that it can be produced and operated without an inert atmosphere, and the prepared electrodes and electrolyte layers are air stable.
  • the electrode in the present invention refers to an electrode used in secondary batteries, especially lithium/lithium ion secondary batteries (including all solid-state batteries and liquid-phase batteries).
  • the present invention provides an electrode, the components of which mainly include: solid electrolyte material, electrode material, conductive agent and binder;
  • the solid electrolyte material can choose to have materials shown in Li a MX b , where M is one or more of Al, Ho, Ga, In, Sc, Y, and La, and X is F, Cl, One or more of Br, 0 ⁇ a ⁇ 10, 1 ⁇ b ⁇ 13.
  • the solid electrolyte material may be selected from one or more of Li 3 InCl 6 , Li 3 YCl 6 , Li 3 YBr 6 , Li 3 HoCl 6 , Li 3 ScCl 6 and the like.
  • the electrode material is a positive electrode material or a negative electrode material; further, the positive electrode material can be LiCoO 2 , NMC (nickel cobalt manganese ternary lithium ion oxide material), LiFePO 4 and other traditional oxide positive electrode materials, or It can also be sulfur, lithium sulfide (Li 2 S), sulfurized polyacrylonitrile and other sulfur cathode materials; the anode material can be graphite, silicon and other anode materials.
  • the positive electrode material can be LiCoO 2 , NMC (nickel cobalt manganese ternary lithium ion oxide material), LiFePO 4 and other traditional oxide positive electrode materials, or It can also be sulfur, lithium sulfide (Li 2 S), sulfurized polyacrylonitrile and other sulfur cathode materials; the anode material can be graphite, silicon and other anode materials.
  • the conductive agent can be a conventional choice in the field, such as one or more of conductive carbon black, carbon nanotube, acetylene black, graphene and the like.
  • the binder can be a conventional choice in the field, for example, it can be an aqueous binder such as an aqueous dispersion of acrylonitrile multi-polymer copolymer (LA 132, LA133, etc.), sodium carboxymethyl cellulose (CMC) and styrene-butadiene Rubber (SBR), sodium alginate (SA), or oily binders such as polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), etc.
  • aqueous binder such as an aqueous dispersion of acrylonitrile multi-polymer copolymer (LA 132, LA133, etc.), sodium carboxymethyl cellulose (CMC) and styrene-butadiene Rubber (SBR), sodium alginate (SA), or oily binders such as polyvinylidene fluoride (PVDF), polyvinylpyrrolidone (PVP), etc.
  • PVDF polyvin
  • the electrode of the present invention may also include other functional additives commonly used in the art.
  • the electrode of the present invention also includes a current collector, which can be a conventional choice in the field.
  • the current collector can be made of aluminum foil (positive electrode), aluminum mesh (positive electrode), carbon-coated aluminum foil (positive electrode), carbon paper (positive and negative electrode), stainless steel (positive and negative electrode), titanium mesh (positive and negative electrode) or copper foil (negative electrode) ).
  • the content of the electrode material in the electrode provided by the present invention may range from 50% to 98% by weight, preferably 70% to 95% by weight; and/or, the content of the solid electrolyte material may range from 2% to 50% by weight, preferably It is 5 wt% to 30 wt%, and/or the content of the conductive agent may be from 1 wt% to 10%, and/or the content of the binder may be from 1 wt% to 10 wt%.
  • the solvent used in the pulping process can be water, or one or more of organic solvents such as ethanol, NMP, n-heptane, etc.; the prepared slurry can be vacuum dried at 50-300°C.
  • the slurry preparation process does not require inert atmosphere protection; an inert atmosphere such as nitrogen and Ar gas can also be used.
  • the slurry preparation process can be carried out in the drying room or not in the drying room.
  • the electrode material of the present invention can be commercialized LiCoO 2 , NMC and other traditional electrode materials without additional surface coating. It can also be a coated electrode material.
  • the electrode material used may not need to undergo a special surface coating, or may be modified by a surface coating layer.
  • the surface coating layer may be a surface coating obtained by ALD deposition, including Li-Nb-O, Li-Ta-O, Li-PO, Li-Si-O, Li-Ti-O; it can also be a surface coating material synthesized by sol-gel method and obtained by molecular layer deposition technology
  • the surface coating layer includes but is not limited to aluminum polyethylene glycol (Alucone), polyuric acid (ployurea), poly 3,4-ethylenedioxythiophene (PEDOT); it can also be a surface synthesized by a sol-gel method
  • the coating layer includes, but is not limited to, Li-Nb-O, Li-Ta-O, and Li-Nb-Ta-O.
  • the electrode material is coated in the solid electrolyte material; wherein the weight ratio of the electrode material to the solid electrolyte material is 95:5, 90:10, 85:15 , 80:20, 70:30, more preferably 85:15.
  • the electrode provided by the present invention has the advantage of encapsulating the electrode material in the solid electrolyte material in that it improves the solid-solid contact between the solid electrolyte and the electrode, and improves the utilization of the electrode active material in the solid battery. , Reducing the electrolyte content in the solid electrode in the electrode, thereby increasing the energy density of the all-solid battery.
  • the preparation method of coating the electrode material in the solid electrolyte material to form a composite electrode material is as follows:
  • Dissolving the solid electrolyte material or its precursor, and electrode material in an organic solvent ultrasonically dispersing, drying (for example, drying at 100°C), and then further vacuum desolventizing and drying (for example, at 200°C; For example, the time is about 5 hours).
  • the electrode provided by the present invention can be prepared by conventional methods in the field. In the preparation method, inert atmosphere protection is usually not needed in the whole preparation process, which is convenient for actual production operation. The existing sulfide electrolyte must be operated and produced under an inert atmosphere.
  • the present invention can also directly start from the precursor and directly coat the halide electrolyte material on the electrode material in situ.
  • the sulfide electrolyte is a solid electrolyte synthesized under harsh conditions, and then dispersed in the electrode.
  • the in-situ coating method proposed by the present invention is more simple and convenient, and improves the solid-solid contact between the electrode material and the electrolyte.
  • the advantage of the electrode provided by the present invention is that the solid electrolyte material has a good solid-solid contact with the electrolyte, the utilization rate of the active material is close to 100%, and the solid electrolyte content in the electrode is less ( ⁇ 15%) (current literature The reported solid electrolyte content in solid-state electrodes is nearly 30%). In the electrodes of all solid-state batteries, reducing the solid electrolyte content will significantly increase the energy density of the battery.
  • the electrode provided by the present invention can be made into a conventional shape or form in the field as required.
  • the present invention also provides an electrolyte thin layer, which mainly includes a solid electrolyte material and a bonding agent; wherein the solid electrolyte material and the bonding agent may have the same meaning as above.
  • the solvent used in the preparation process can also be the same as above.
  • the outstanding advantage of the thin electrolyte layer provided by the present invention lies in its small thickness, which is usually less than 50 microns. In some specific embodiments of the present invention, the thickness of the provided electrolyte thin layer is 20-200 microns.
  • the thin electrolyte layer of the present invention has a relatively low thickness, its use in a solid-state battery can significantly increase the energy density of an all-solid-state battery.
  • the thin electrolyte layer of the present invention can be prepared by conventional methods in the field; the preparation process does not require inert atmosphere protection.
  • the preparation of the thin electrolyte layer can be achieved by using an aqueous phase or an organic phase as the solvent and adhesive.
  • the preparation method of the thin electrolyte layer is as follows:
  • the binder is dissolved in a solvent, and then the solid electrolyte material or its precursor (such as LiCl, MCl 3 ) and a conductive agent are added to form a slurry (the concentration of the slurry can be adjusted by adjusting the amount of the solvent), and then coated It is clothed on a current collector or a flexible substrate, dried (for example, vacuum-dried under the adjustment of 100-110°C), and then peeled off from the current collector or flexible substrate.
  • the solid electrolyte material or its precursor such as LiCl, MCl 3
  • a conductive agent a slurry
  • the concentration of the slurry can be adjusted by adjusting the amount of the solvent
  • It is clothed on a current collector or a flexible substrate, dried (for example, vacuum-dried under the adjustment of 100-110°C), and then peeled off from the current collector or flexible substrate.
  • the current collector may be copper foil; the flexible substrate may be nickel mesh, PEO film, or the like.
  • the content of the solid electrolyte material may range from 20 wt% to 100 wt%, preferably 45 wt% to 99 wt%; the content of the binder may range from 0 to 80 wt%, preferably 1 wt% To 55wt%;
  • the electrolyte thin layer provided by the present invention can adopt a flexible substrate, such as PEO film, glass fiber, etc., as a self-supporting film.
  • the present invention also includes the application of the solid electrolyte material as described above in preparing electrodes or electrolyte thin layers.
  • the solid electrolyte material provided by the present invention can be synthesized in an aqueous solution. There is no report that solid electrolyte can be synthesized in water phase.
  • a water-based binder and water can be used as a solvent to synthesize a solid electrolyte, or water can be used to make a solid electrode and a solid electrolyte layer. Low cost and environmentally friendly.
  • the solid electrolyte material composed of Li 3b-3a In a Cl 3 please refer to the above and the following embodiments and drawings for details.
  • the present invention also includes the application of the above-mentioned electrode or the above-mentioned electrolyte thin layer in the preparation of batteries, especially secondary batteries, especially lithium/lithium ion secondary batteries (including all solid-state batteries and liquid-phase batteries).
  • the present invention also provides a secondary battery, particularly a lithium/lithium ion secondary battery (including all solid-state batteries and liquid-phase batteries), which includes the above-mentioned electrode or the above-mentioned electrolyte thin layer; and also includes other conventional components of the secondary battery.
  • a secondary battery particularly a lithium/lithium ion secondary battery (including all solid-state batteries and liquid-phase batteries), which includes the above-mentioned electrode or the above-mentioned electrolyte thin layer; and also includes other conventional components of the secondary battery.
  • the electrode can be coated with water as a solvent
  • the ion conductance can reach above 1.5 ⁇ 10 -3 S/cm
  • a solid electrolyte can be synthesized in situ on the electrode material (one-step method) to form a structure where the solid electrolyte covers the electrode material, thereby improving the solid-solid contact between the electrode and the solid electrolyte, and improving the active material in the all-solid battery
  • the utilization rate reduces the solid electrolyte content in the solid electrode, thereby increasing the energy density of the solid battery.
  • the present invention adopts an air-stable, high-ion-conducting, and easy-to-matrix solid electrolyte material as an ion-conducting additive for all-solid-state batteries; and due to solid electrolyte materials and oxide electrode materials (such as LCO, NMC, etc.)
  • solid electrolyte materials and oxide electrode materials such as LCO, NMC, etc.
  • oxide electrode materials such as LCO, NMC, etc.
  • Figure 3 is a curve of the value of the glass-ceramic phase Li 3 Y 1-d In d Cl 6 additive d and the corresponding product ion conductance change curve in Example 1.1.
  • Figure 4 is an X-ray diffraction pattern of the crystalline phase Li 3 InCl 6 in Example 1.2;
  • Figure 5 is a graph of the temperature-variable ion conductivity of the crystalline phase Li 3 InCl 6 in Example 1.2;
  • Fig. 6 is the charge and discharge curve of the all-solid LiIn-LiCoO 2 secondary battery in Application Example 1.1.
  • Fig. 7 is a charging and discharging curve of an all-solid LiIn-NMC811 secondary battery in Application Example 1.1.
  • Fig. 8 is a charging and discharging curve of application example 1.2 liquid phase Li-LCO secondary battery
  • Figure 10 is a temperature-variable ion conductivity diagram of Li 4 InCl 7 obtained in an aqueous solution in Example 2.1;
  • Figure 11 is a graph of the temperature-variable ion conductivity of Li 3 InCl 5 F obtained in an aqueous solution in Example 2.2;
  • Example 12 is a graph showing the relationship between the room temperature ionic conductivity of Li 1-3z In z Cl (0.1 ⁇ z ⁇ 0.25) obtained in Example 2.3 as a function of z;
  • Example 13 is an X-ray diffraction diagram of the glass-ceramic phase Li 3 In 0.8 Y 0.2 Cl 6 solid electrolyte material obtained in Example 2.5;
  • Example 14 is a graph of temperature-variable ionic conductivity of the glass-ceramic phase Li 3 In 0.8 Y 0.2 Cl 6 solid electrolyte material obtained in Example 2.5;
  • Example 15 is an X-ray diffraction diagram of the glass-ceramic phase Li 2 In 0.1 Zn 0.9 Cl 4.1 solid electrolyte material obtained in Example 2.6;
  • Example 17 is the impedance curve of the glass-ceramic phase LiGaCl 4 solid electrolyte material obtained in Example 2.7 at room temperature;
  • Figure 19 is the impedance curve of the glass-ceramic phase Li 6 FeCl 8 solid electrolyte material obtained in Example 2.8 at room temperature;
  • Example 20 is an X-ray diffraction diagram of the glass-ceramic phase Li 3 YCl 6 solid electrolyte material obtained in Example 2.9;
  • Example 21 is a graph of the temperature-variable ion conductivity of the glass-ceramic phase Li 3 YCl 6 solid electrolyte material obtained in Example 2.9;
  • Figure 22 is the charge and discharge curve of the all-solid LiIn-LiCoO 2 secondary battery in Application Example 2.1.
  • Figure 23 is the charging and discharging curve of the all-solid LiIn-NMC811 secondary battery in Application Example 2.1;
  • Fig. 24 is an X-ray diffraction diagram of the Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1 and its corresponding structure refinement;
  • Figure 25 is the synchrotron radiation X-ray absorption spectrum of Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1 and its fitted structure model;
  • Figure 26 is the crystal structure and atomic distribution diagram of the Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1;
  • Figure 27 is an electrochemical characterization of the Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1.
  • a is the variable temperature impedance curve of the material and its corresponding ion conductivity,
  • b is the voltage window test curve of the material;
  • Figure 28 is the charge and discharge curve of the all-solid LiIn-LiCoO 2 secondary battery in Application Example 3.1;
  • Figure 29 is an application example 3.1 all solid state LiIn-NMC811 secondary battery charge and discharge curve
  • FIG. 30 shows the process of forming Li 3 InCl 6 coated LiCoO 2 cathode material in the water phase in Example 4.1 and the prepared material;
  • Figure 31 shows the process of forming Li 3 InCl 6 coated LiCoO 2 cathode material in situ in the water phase in Example 4.2 and the prepared material;
  • Figure 32 shows the process of forming Li 3 InCl 6 coated NMC532 cathode material from the organic phase in Example 4.3 and the prepared material;
  • FIG. 33 shows the process of in-situ formation of Li 3 InCl 6 coated NMC532 cathode material in the organic phase in Example 4.4 and the prepared material;
  • Figure 34 shows the process of preparing an organic phase coating electrode material and the materials prepared in Example 4.5;
  • 35 shows the process of preparing the organic phase coating electrolyte layer and the materials prepared in Example 4.6.
  • the grinding is carried out in a glove box, either manual grinding or machine grinding; the ball milling operation can be carried out in a zirconia ball mill tank, usually a sealed ball mill.
  • Example 1.1 Glass-ceramic phase Li 3 Y 1-d In d Cl 6 additive and its preparation
  • Figure 3 shows the above-mentioned value of d and the corresponding product ion conductance change curve.
  • Figures 4 and 5 are the X-ray diffraction diagrams and temperature-variable ion conductivity diagrams of the crystalline phase Li 3 InCl 6 prepared in this example.
  • the preparation method is similar to that of Example 1.1, except that the raw materials used are as follows: 30 millimoles of LiCl (1.29 g) and 2.7 g of NbCl 5 ; the ball milling speed is changed to 450 rpm, and the ball milling time is 10 hours. After the precursor is ball milled, the glass phase Li 3 NbCl 8 additive can be obtained.
  • Example 1.4 Glass-ceramic phase Li 3 YCl 6 electrode additive material and its preparation
  • Unmodified LiCoO 2 and NMC811 are used as cathode materials.
  • the positive electrode material: crystalline phase Li 3 InCl 6 electrode additive material was mixed at a ratio of 70:30 (mass ratio). The mixing process was carried out in a glove box, and the specific process was grinding with a mortar for 20 minutes. The ground material is used as a positive electrode powder. A thin metal indium sheet is used as the negative electrode, and the electrolyte also uses a commercial Li 10 GeP 2 S 12 electrolyte material. Take 100 mg of Li 10 GeP 2 S 12 electrolyte material into a mold battery liner with a cross-sectional area of 0.785 square centimeters, and press tablets at a pressure of 200 MPa to obtain an electrolyte layer.
  • Figure 6 shows the charge and discharge curve of the battery for 1-5 cycles.
  • the first cycle charge capacity is 142 mAh per gram of lithium cobalt oxide
  • the first cycle discharge capacity is 131 mAh per gram of lithium cobalt oxide, corresponding to the first cycle of Coulomb
  • the efficiency is 91.7%.
  • the battery capacity stabilized at about 130 mAh per gram of lithium cobalt oxide, and the reversibility of battery cycles was better.
  • the all-solid LiIn-NMC811 battery is charged and discharged with a current density of 100 microamperes, and the cut-off voltage is 1.9-3.9 volts.
  • Fig. 7 is the charging and discharging curve diagram of the battery in the first lap.
  • the first lap charge capacity is 231 mAh per gram of NMC811
  • the first lap discharge capacity is 192 mAh per gram of NMC811
  • the corresponding first lap Coulomb efficiency is 83.1%.
  • Unmodified LiCoO 2 is used as the cathode material.
  • the positive electrode material crystalline phase Li 3 InCl 6 electrode additive material was mixed at a ratio of 90:10 (mass ratio). The mixing process was carried out in a glove box, and the specific process was grinding with a mortar for 20 minutes. The ground material is used as a positive electrode powder. 85% by weight of positive electrode powder, 10% by weight of PVDF adhesive and 5% by weight of conductive carbon black are used for stirring and pulping, and NMP is used as the solvent for pulping. The obtained slurry is coated on the metal aluminum foil.
  • the positive electrode sheet can be obtained by drying in a vacuum at 100°C.
  • the thickness of the pole piece is greater than 400 microns, and the load of the single-sided LCO is greater than 20 mg/cm2.
  • the lithium sheet is used as the counter electrode, the polyolefin porous membrane (Celgard 2500) is used as the separator, and the mixed solution of LiPF 6 ethylene carbonate (EC) and dimethyl carbonate (DMC) (volume ratio 1:1) is used as the electrolyte.
  • the CR2016 battery is assembled in a glove box in an argon atmosphere. The electrical performance test is performed at a test temperature of 25°C.
  • Figure 8 shows the charging and discharging curve of the battery in the first lap.
  • the charging capacity in the first lap is 139 mAh per gram of LCO and the discharge capacity in the first lap is 129 mAh per gram of LCO.
  • the above experimental results show that the lithium secondary battery additive provided by the present invention can improve the electrode ion transmission speed and is compatible with existing lithium secondary battery electrode materials.
  • the material has high room temperature ion conductivity, stable air, simple preparation method, and compatibility with existing lithium secondary battery electrode materials. It is expected to solve the problems of slow ion transmission of electrode materials in lithium secondary batteries, low electrode material load, and difficulty in further increasing the electrode thickness, so that it is expected to realize the preparation of electrode pads with high energy density and low electrode polarization, and further improve Energy density of lithium secondary batteries.
  • 9 and 10 are the X-ray diffraction patterns and temperature-variable ion conductivity diagrams of the glass-ceramic phase Li 4 InCl 7 solid electrolyte material prepared in this embodiment, respectively.
  • Example 2.1 Similar to Example 2.1, the difference is that 40 mmol of LiCl (1.7 g) precursor is changed to a mixture of 20 mmol of lithium chloride (0.85 g) and 10 mmol of lithium fluoride (0.26 g). The annealing temperature was changed to 400°C. The sample obtained after annealing is a glass-ceramic phase Li 3 InCl 5 F solid electrolyte material.
  • FIG. 11 is a graph of the temperature-variable ion conductivity of the glass-ceramic phase Li 3 InCl 5 F solid electrolyte material prepared in this embodiment.
  • FIG. 12 is a graph showing the relationship between room temperature ion conductivity and z of the glass-ceramic phase Li 1-3z In z Cl (0.1 ⁇ z ⁇ 0.25) solid electrolyte material prepared in this embodiment.
  • Figures 13 and 14 are the X-ray diffraction diagrams and temperature-variable ion conductivity diagrams of the glass-ceramic phase Li 3 In 0.8 Y 0.2 Cl 6 solid electrolyte material prepared in this embodiment.
  • Figure 15 is an X-ray diffraction diagram of the glass-ceramic phase Li 2 In 0.1 Zn 0.9 Cl 4.1 solid electrolyte material prepared in this embodiment.
  • Figures 16 and 17 are respectively the X-ray diffraction pattern and the impedance curve of the glass-ceramic phase LiGaCl 4 solid electrolyte material prepared in this embodiment at room temperature. It can be calculated from Figure 17 that the room temperature ion conductivity of the material is 9*10 -5 S/cm.
  • Figures 18 and 19 are respectively the X-ray diffraction pattern and the impedance curve under room temperature conditions of the glass-ceramic phase Li 6 FeCl 8 solid electrolyte material prepared in this embodiment. It can be calculated from Figure 19 that the room temperature ion conductivity of the material is 5*10 -6 S/cm.
  • Figures 20 and 21 are the X-ray diffraction patterns and temperature-variable ion conductivity diagrams of the glass-ceramic phase Li 3 YCl 6 solid electrolyte material prepared in this embodiment.
  • Application Example 2.1 Application of the glass-ceramic phase Li 4 InCl 7 solid electrolyte material prepared in Example 2.1 in all-solid LiIn-LiCoO 2 , LiIn-LiNi 0.8 Mn 0.1 Co 0.1 O 2 (LiIn-NMC811).
  • Unmodified LiCoO 2 and NMC811 are used as cathode materials.
  • the cathode material: the glass-ceramic phase Li 4 InCl 7 solid electrolyte material obtained in Example 2.1 is mixed at a ratio of 90:10 (mass ratio).
  • the mixing method is manual grinding for 5 minutes.
  • the mixing process is It is carried out in an air atmosphere, the ground sample is placed in a 20 ml glass instrument bottle, and deionized water of five times the mass of the sample is added for dispersion, and then placed in an ultrasonic instrument for 5 minutes. After the ultrasound, the glass instrument bottle was placed in a vacuum drying box and dried at 80°C for 12 hours in a vacuum environment.
  • the sample obtained after drying is the positive electrode powder of the secondary battery.
  • a thin metal indium sheet is used as the negative electrode, and the electrolyte also uses a glass-ceramic phase Li 4 InCl 7 solid electrolyte material and a commercial Li 10 GeP 2 S 12 electrolyte material.
  • 50 mg of Li 10 GeP 2 S 12 electrolyte material is placed on one end of the first electrolyte layer, and the tablet is pressed at a pressure of 200 MPa to obtain a double-layer electrolyte layer.
  • FIG. 22 is a graph showing the charge and discharge curves of the battery.
  • the all-solid LiIn-NMC811 battery is charged and discharged with a current density of 100 microamperes, and the cut-off voltage is 1.9-3.9 volts.
  • Fig. 23 is a graph showing the charging and discharging curve of the first round of the battery.
  • Application Example 2.2 Application of the glass-ceramic phase Na 3 InCl 4 Br 2 solid electrolyte material prepared in Example 2.4 in an all-solid sodium secondary battery
  • the cathode material glass-ceramic phase Na 3 InCl 4 Br 2 solid electrolyte material: conductive carbon black is mixed at a ratio of 80:15:5 (mass ratio).
  • the mixing process is carried out in a glove box. The specific process is adopted Grind in a mortar for 20 minutes.
  • the ground material is used as a positive electrode powder.
  • the tin sheet is used as the negative electrode, and the glass-ceramic phase Na 3 InCl 4 Br 2 solid electrolyte material is used as the electrolyte.
  • the following ionic conductivity method uses AC impedance to test, the test method is: weigh 150 mg of electrolyte material in the glove box, then press the tablet in the mold battery, the pressure is 350MPa, and then measure the thickness of the electrolyte layer as L , Then directly assemble a carbon/electrolyte/carbon symmetrical battery in the mold battery, measure the AC impedance of the battery under the open circuit condition, and record the impedance value as R.
  • ⁇ L/(R ⁇ A) to calculate, Where ⁇ is the ionic conductivity, L is the thickness of the electrolyte layer, R is the impedance value, and A is the electrode area of the electrolyte sheet.
  • FIG. 24 is an X-ray diffraction diagram of the glass-ceramic phase Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in this embodiment and its corresponding structure refinement;
  • FIG. 25 shows the synchrotron radiation X-ray absorption spectrum of the glass-ceramic phase Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in this embodiment and its fitted structure model.
  • indium ions are arranged at In 1 (0,0.333,0) and In 2 (0,0,0) positions, The proportion of indium ions at the In 1 position is 7%, and the proportion of indium ions at the In 2 position is 87.5%. See Table 1 below for details.
  • indium ions are all arranged in the In 1 (0,0.333,0) position, accounting for 53%. See Table 2 below for details.
  • 26 is a diagram of the crystal structure and atomic distribution of the Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in this embodiment;
  • Fig. 27a shows the temperature-varying impedance curve and the corresponding ion conductivity of the Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in this embodiment.
  • the ionic conductivity of the material is 2mS/cm at room temperature;
  • Figure 27b is the voltage window test curve of the Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in this embodiment.
  • the test method uses Li/electrolyte/Au battery to cycle volts. Ann’s test method is carried out.
  • Application Example 3.1 Application of the glass-ceramic phase Li 1.5 In 0.53 Cl 3 solid electrolyte material prepared in Example 3.1 in all solid LiIn-LiCoO 2 , LiIn-LiNi 0.8 Mn 0.1 Co 0.1 O 2 (LiIn-NMC811).
  • Unmodified LiCoO 2 and NMC811 are used as cathode materials.
  • the cathode material: the glass-ceramic phase Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1 is mixed at a ratio of 70:30 (mass ratio).
  • the mixing method is manual grinding for 5 minutes.
  • the mixing process It is carried out in a glove box, and the obtained sample is the positive electrode powder of the secondary battery.
  • a thin metal indium sheet was used as the negative electrode, and the glass-ceramic phase Li 1.5 In 0.53 Cl 3 solid electrolyte material obtained in Example 3.1 and the commercial Li 10 GeP 2 S 12 electrolyte material were also used as the electrolyte.
  • Fig. 28 is a charging and discharging curve diagram of an all-solid LiIn-LiCoO 2 battery.
  • Fig. 29 is a graph showing the first round charge and discharge curve of an all-solid LiIn-NMC811 battery.
  • the Li 3 InCl 6 75mg of 2g was dissolved in water and then added 425mg of LiCoO 2, in a dry 100 deg.] C, and transferred to a 200 °C further dried in a vacuum oven, to give L i3 InCl 6 coated LiCoO 2; No inert atmosphere protection is needed during the whole experiment.
  • (a) represents the specific synthesis process; Heating represents heating, and Vacuum represents vacuum conditions; (b, c) represent SEM photos of LiCoO 2 before coating; (d, e) represent SEM photos of LiCoO 2 after coating .
  • (a) represents the specific synthesis process; Heating represents heating and Vacuum represents vacuum conditions; (b) SEM photos of LiCoO 2 before coating; (c, d) SEM photos of LiCoO 2 after coating; (e) First charge-discharge curve of LiCoO 2 coated with different content of Li 3 InCl 6 ; (f) Cycle stability of LiCoO 2 coated with different content of Li 3 InCl 6 .
  • the abscissa of (e) represents the specific discharge capacity, and the ordinate represents the voltage to the metal lithium negative electrode; the current density of constant current charge and discharge is 0.13 mA/cm 2 .
  • the abscissa indicates the number of cycles, the ordinate on the left indicates the specific discharge capacity, and the ordinate on the right indicates the Coulomb efficiency.
  • the current density of the cycle test is 0.13mA/cm 2 .
  • the experimental samples in (e) and (f) are LiCoO 2 electrodes coated with Li 3 InCl 6 with different mass ratios (05:95, 10:10, 15:85) synthesized according to the above method.
  • the electrochemical test results showed that the first discharge specific capacity of the LiCoO 2 electrode containing 15% Li 3 InCl 6 was 131 mAh/g. After 60 cycles, it remained at 106.4 mAh/g.
  • the LiCoO 2 electrode containing 10% Li 3 InCl 6 The first discharge specific capacity is 91.6mAh/g. After 60 cycles, it remains at 64.7mAh/g.
  • the LiCoO 2 electrode containing 5% Li 3 InCl 6 has a first discharge specific capacity of 40.1mAh/g. After 60 cycles, it remains at 12.9 mAh/g.
  • Li 3 InCl 6 and 425 mg of NMC532 were dissolved in 2 g of ethanol, dispersed ultrasonically for 5 minutes, then transferred to a 100-degree oven for drying, and then transferred to a 200-degree vacuum oven for further desolventization and drying.
  • Li 3 InCl 6 to obtain coated NMC532 (NMC532 and Li 3 InCl 6 mass ratio of 85:15), throughout the experiment without inert atmosphere protection.
  • the mass ratios of NMC532 and Li 3 InCl 6 were controlled to 80:20 and 90:10 according to the same method, and NMC532 coated with different content of Li 3 InCl 6 was prepared.
  • (a) represents the specific synthesis process; Ethanol represents ethanol, Heating represents heating, and Vacuum represents vacuum conditions; (b) SEM photos of SC-NMC532 before coating; (c,d) SC-NMC532 after coating SEM photos; (e) first charge-discharge curves of LiCoO 2 coated with different content of Li 3 InCl 6 ; (f) cycle stability of LiCoO 2 coated with different content of Li 3 InCl 6 .
  • the abscissa of (e) represents the specific discharge capacity, and the ordinate represents the voltage to the metal lithium negative electrode.
  • the current density of constant current charging and discharging is 0.13mA/cm 2 .
  • the abscissa indicates the number of cycles, the ordinate on the left indicates the specific discharge capacity, and the ordinate on the right indicates the Coulomb efficiency.
  • the current density of the cycle test is 0.13mA/cm 2 .
  • the experimental samples in (e) and (f) are Li 3 InCl 6 coated SC-NMC532 electrodes synthesized according to the above method, wherein the mass ratio of Li 3 InCl 6 and SC-NMC532 is 15%:85wt%. SC stands for single crystal.
  • the electrochemical test results show that the specific discharge capacity of SC-NMC532 in Li 3 InCl 6 electrolyte for the first time is as high as 159mAh/g, and after 10 cycles, the gram capacity remains at 137.6mAh/g.
  • FIG 34 shows the process of preparing the slurry and the process of coating the slurry; (b) shows the pole piece obtained after drying; (c) shows the coating of the slurry prepared in this embodiment on the carbon-coated aluminum foil Compared with the upper electrochemical performance of conventional aluminum foil.
  • the abscissa of (c) represents the specific discharge capacity, and the ordinate represents the voltage to the metal lithium negative electrode.
  • the current density of constant current charging and discharging is 0.13mA/cm 2 .
  • the experimental samples are aluminum foil (Al) and carbon-coated aluminum foil current collector (C-coated Al), and CC stands for current collector. The test results showed that the electrode coated with carbon-coated aluminum foil showed less polarization.
  • the invention discloses a lithium secondary battery additive, battery and electrode.
  • the lithium secondary battery additive provided by the invention has high ion conductivity and air stability, can improve the rapid transmission of electrode ions, increase the electrode load and thickness, and increase the energy density of the battery.
  • the solid electrolyte material provided by the present invention has high lithium ion conductivity.
  • the electrode and electrolyte thin layer provided by the invention can significantly improve ionic conductivity, chemical/electrochemical stability and plasticity.
  • the invention has broad application prospects and good industrial applicability in the technical field of secondary batteries.

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Abstract

锂二次电池固态电解质材料、电极及电池，具体涉及一种具有改善锂二次电池电极离子快速传输的添加剂材料、及其制备方法与应用，二次电池固态电解质材料及其制备方法与应用，以及一种电极、电解质薄层及其制备方法。

Description

锂二次电池固态电解质材料、电极及电池
相关申请的交叉引用
本申请要求于2019年4月29日提交的申请号为201910354433X，名称为“锂二次电池添加剂及其制备方法与应用”、于2019年5月8日提交的申请号为2019103811538，名称为“二次电池固态电解质材料及其制备方法与应用”、于2019年9月6日提交的申请号为2019108433475，名称为“固态电解质材料和全固态电池”以及于2019年9月6日提交的申请号为2019108434054，名称为“电极、电解质薄层及其制备方法”的中国专利申请的优先权，其所公开的内容通过引用全部并入本文。
技术领域
本发明涉及锂二次电池添加剂、电池及电极，具体涉及一种具有改善锂二次电池电极离子快速传输的添加剂材料及其制备方法与应用，二次电池固态电解质材料及其制备方法与应用，以及一种电极、电解质薄层及其制备方法。
背景技术
当谈论到电池的能量密度时，锂二次电池是一个理想的电池体系。然而，到目前为止，锂二次电池的电化学性能仍然受限于电极层中的离子以及电子的传输速率。在锂二次电池电极制备过程中，电极的电子传输通道主要依靠添加导电碳等电子高传导材料进行提供。另一方面，电极的离子传输通道的提供，有机相的锂二次电池与全固态的锂二次电池的方法是不一样的。由于有机电解质具有高渗透性以及浸润能力，因此在电极制备过程中通过在电极层中预留孔隙等方式，实现电解质在电极层中的浸润而实现离子在电极层中的传输。该方法虽然避免了额外材料的添加，然而，大量孔隙的存在对于电池的能量密度的降低也是非常显著的。同时，该方法难以获得较厚的电极层，进一步的限制了电极活性材料的负载量。在全固态电池中，因为固态电解质不具有流动性，电极活性颗粒与电解质之间的浸润接触问题比液相电池要复杂。因此，应用于全固态电池的电极层需要 额外的添加快离子材料以获得快速的离子通道，目前常用的都是添加相应的固态电解质材料。然而，目前固态电解质所存在的与电极材料化学兼容的问题，固态电解质的空气稳定性以及溶剂稳定性等方面的问题以及固态电解质制备工艺等问题使得固态电解质材料难以直接应用于电极成膜工艺过程中。
发明内容
本发明首先提供一种锂二次电池添加剂，其具有高的离子电导率以及空气稳定性,能够改善电极离子快速传输，提高电极负载量和厚度，并与现有锂二次电池电极材料相兼容，有望解决锂二次电池中电极材料离子传输较慢、电极材料负载低，电极厚度难以进一步提高等方面的问题，从而有望实现具有高能量密度以及低电极极化的电极极片的制备，进一步提高锂二次电池的能量密度。同时，该锂二次电池添加剂室温离子传导率较高，空气稳定，制备方法简单。
具体而言，本发明提供一种如下式所示的锂二次电池添加剂，
Li bM aX c，
其中，M选自B,Al,Ga,In,Y,Sc,Sb,Bi,Nb,Ta,Ti,Zr,V,Cr,Mo,W,Mn,Tc,Re,Fe,Co,Ni,Cu,Ag,Zn,Cd,La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu中的一种或者多种；X选自F,Cl,Br,I中的一种或者多种；0.2≤b≤6；0.1≤a≤3；1≤c≤9。
在本发明具体实施方式中，b可选自0.2,0.5,1,2,3,4,5或6，进一步优选地，1≤b≤3。
在本发明具体实施方式中，a可选自0.1,0.2,0.5,1,1.5,2，2.5或3，进一步优选地，0.2≤a≤1。
在本发明具体实施方式中，c可选自1,2,3,4,5,6,7,8或9，进一步优选地，3≤c≤6。
在本发明一些优选实施方式中，所述锂二次电池添加剂如下所示，
Li 3Y 1-dIn dCl 6，(玻璃-陶瓷相)；其中，0≤d≤1；进一步地，d选自0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9或1.0。
进一步地，本发明所述锂二次电池添加剂可为玻璃相、玻璃-陶瓷相或结晶相。
在本发明另一些优选实施方式中，所述锂二次电池添加剂如下所示，
Li 3InCl 6(结晶相)、Li 3NbCl 8(玻璃相)、Li 3YCl 6(玻璃-陶瓷相)。
本发明上述锂二次电池添加剂均可按本领域常规技术制备。
例如可将所需原料(或前驱物)按配比混合后研磨而制得；或者进一步采用有机溶剂共溶重结晶法，加热共熔法，不溶性烃类有机溶剂中使原料颗粒相接触的方法制成相应相态的化合物。
进一步地，制备本发明所述锂二次电池添加剂的原料(或前驱物)包括LiX和MX y前驱物，其中M、X的定义与上文相同；1≤y≤6，优选地，2≤y≤5。例如具体地，y可选自1,2,3,4,5,或6。
具体地，所述混合可以使用球、珠的方式进行混合，也可以在非球、珠的方式下进行混合。可以在有机溶剂中进行混合，也可以以不使用有机溶剂的方式进行混合。
进一步地，所述有机溶剂可以是极性溶剂，也可以是非极性溶剂。溶剂可以溶解、部分溶解以及不溶解上述LiX和MX y前驱物。作为非极性溶剂，可以列举出烃类溶剂和醚类溶剂。作为该烃类溶剂，可以列举出脂肪族烃类溶剂以及芳香性烃类溶剂。优选为脂肪族烃类溶剂，进一步优选为己烷。作为该醚类溶剂，可以列举出环酯类溶剂和链式酯类溶剂，优选为环酯类溶剂，进一步优选为四氢呋喃。
进一步地，在制备本发明所述锂二次电池添加剂过程中，例如在所需原料(或前驱物)混合过程中可以采用NH 4Cl、I 2、LiI、S等材料作为助溶剂、助熔剂或者络合物的配体进行使用。其优点在于可以降低反应温度，形成配合物中间体等利于产物的获取。
进一步地，本发明中可以通过加热退火的方法将所获得的玻璃相或玻璃-陶瓷相中间产物转变为玻璃-陶瓷相或结晶相。
其中，所述加热退火温度为100-600℃，优选150-350℃。所述加热退火时间通常为10分钟-24小时，优选1-10小时。加热退火可以在空气、氮气、氩气等气氛中进行，也可以在真空气氛中进行。
进一步地，所述加热退火过程中还可以加入NH 4Cl、I 2、LiI、S、P、二茂铁等易挥发材料进行物相和形貌的调控。其优点在于降低退火温度，同时有利于提高材料离子传导率。
本发明还包括上述方法制备的锂二次电池添加剂。
本发明还包括上述锂二次电池添加剂在锂二次电池中作为电极添加剂的应用，或者在制备锂二次电池中的应用。采用本发明所述添加剂可以改善电极离子传输速度，并与现有锂二次电池电极材料相兼容。
本发明还提供一种锂二次电池，该电池的正极层、电解质层和负极层中至少一者含有一种或者多种上述锂二次电池添加剂。
本发明中，所述锂二次电池包括液相锂二次电池、半固态以及全固态锂二次电池。
本发明所述锂二次电池可按本领域常规方法进行制备。
本发明提供的锂二次电池添加剂可作为具有改善电极离子快速传输的添加剂材料。相应的，该材料不仅可应用于有机相的锂二次电池中也可以应用于全固态或半固态锂二次电池中。本发明提供的锂二次电池添加剂具有以下优点：
1.本发明所提出的电极添加剂材料在空气条件下稳定，与锂二次电池电极极片制备过程中所使用的溶剂如NMP(氮甲基吡咯酮烷)以及胶黏剂如PVDF(聚偏二氟乙烯)等不发生化学反应。进一步的，与现有锂二次电池电极材料如硫、硫化锂、钴酸锂、锰酸锂、磷酸铁锂、镍锰钴酸锂、高压相镍锰酸锂以及富锂相锰基电极材料等化学相兼容。可以直接应用到现有的成熟的电极制备工艺中。
2.本发明所提出的电极添加剂材料具有室温高离子电导率的特点，在与活性电极材料进行混合后，可以提高锂离子在活性电极材料和电解质之间的快速传导。因此，该材料的添加有利于降低电极片中活性颗粒之间以及活性颗粒与电解质之间的界面阻抗，从而提高锂二次电池的倍率性能以及活性材料的负载量，进一步的有利于提高锂二次电池的能量密度。
3.本发明所提出的电极添加剂材料具有较宽的工作温度以及电化学惰性，电化学窗口达6伏以上，在电池充放电过程中不会分解。同时，该材料制备方法简单，易于在锂二次电池中的使用。
全固态二次电池相较于目前商用的有机相二次电池具有更高的安全性。这是由于全固态二次电池采用了不可燃的固态快离子材料作为电解质。随着近几年的发展，目前已经发展出了几种离子导高于1mS cm -1的固态电 解质材料。这些材料以硫化物以及氧化物电解质为主。其中硫化物电解质包括Li 10Ge 2P 2S 12,Li 6PS 5Cl，Li 7P 3S 11以及Li 3PS 4等；氧化物电解质主要有Li 1.3Al 0.3Ti 1.7(PO 4) 3,Li 7La 3Zr 2O 12等。然而，硫化物电解质在空气以及水中不稳定，易于产生硫化氢等有毒气体，需要在惰性气体为保护气氛的环境下进行操作；氧化物电解质需要在高温条件下才能成相，成相温度在1000℃以上，难以大量制备生产。
为此，本发明还提供一种二次电池固态电解质材料，其离子传导率较高(高于1mS cm -1)，能在空气以及水中稳定，且与商业常用的如LCO,NMC等氧化物正极材料相兼容。有望解决全固态二次电池中固态电解质材料宏量制备时所面临的工艺复杂，费时耗能以及价昂等问题。进一步的可以解决全固态二次电池中固态电解质材料化学以及电化学不稳定等问题。从而实现全固态二次电池的商业应用价值。
具体而言，本发明提供一种如下式所示的二次电池固态电解质材料，
A 1-3zIn zX；
其中，A选自Li、Na、K、Cs中的一种或者多种；X选自F,Cl,Br,I中的一种或者多种；0<z≤0.33。
进一步地，0.1≤z≤0.25；例如具体地，z可选自0,0.25,0.2,0.167,0.143或0.1。
在本发明一些优选实施方式中，所述固态电解质材料如下任一式所示，
Li 4InCl 7；
Li 3InCl 5F；
Li 1-3zIn zCl，z为0.25,0.2,0.167,0.143或0.1；
Na 3InCl 4Br 2。
进一步地，本发明所述固态电解质材料，其中的In可以被以下元素部分或者全部取代而形成新的电解质材料，可取代元素为Al、Ga、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Fe、Bi、Sb、Cr、Co、Zr、Zn、Cd、Mg中的一种或者多种。
在本发明一些优选实施方式中所述固态电解质材料如下任一式所示，Li 3In 0.8Y 0.2Cl 6，或Li 2In 0.1Zn 0.9Cl 4.1，或LiGaCl 4，或Li 6FeCl 8，或Li 3YCl 6，或Li 3BiCl 6。
进一步地，本发明所述固态电解质材料可为玻璃相、玻璃-陶瓷相或结晶相。
进一步地，本发明所述固态电解质材料包含主结晶相，在所述结晶相为扭曲的岩盐相结构。
进一步地，本发明所述固态电解质材料可包含异种晶相，所述异种晶相与主结晶相具有不同的晶体结构排列。
进一步地，本发明所述固态电解质材料可包含非晶相。
通常，本发明上述固态电解质材料均可按本领域常规技术制备。
具体地，本发明上述固态电解质材料采用水相法制备得到。采用的原料(或前驱物)包括但不限于AX、InX 3和MX a；其中A、X的定义与上文含义相同；M为Al、Ga、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Fe、Bi、Sb、Cr、Co、Zr、Zn、Cd、Mg中的一种或者多种；2≤a≤4。
优选地，所述原料AX，InX 3以及MX a可以扩展为其相应的水合物或者溶液。或者，所述原料AX，InX 3以及MX a可以扩展为在水相中游离或反应出具有等同离子作用的前驱物，包括但不限于碳酸盐，碳酸氢盐。
进一步地，上述水相法在制备过程中可以适当加入HCl、NH 4Cl等作为水解抑制剂或者配位剂。
进一步地，上述水相法具体包括：将所需原料或前驱物以一定的比例溶于水相中，所需原料或前驱物与水相的质量比为1:0.5～1:15，优选1:2～1:5。
进一步地，上述水相法可将所需原料或前驱物在室温条件下溶于水相中，待全部组分溶解后，进干燥即可获得所述固态电解质材料。上述干燥的温度通常为60-100℃，可在真空或非真空条件下进行干燥。例如可在在烘箱内进行干燥。
进一步地，上述水相法中在干燥后可进行退火处理，退火温度为100～600℃，优选120～500℃。其优点在于提高材料的结晶度，有利于提高材料的稳定性以及离子传导率。
所述退火在空气气氛中进行，亦可在惰性气体气氛中或者真空气氛中进行。
进一步地，上述制备方法所述水相不仅可以使用去离子水，也可以改用有机溶剂或者是有机溶剂/水的混合溶剂进行扩展。
进一步地，上述制备方法所述有机溶剂为醇类，如乙醇。
本发明还包括上述方法制备的固态电解质材料。
本发明所述固态电解质材料既可以用作二次电池的添加剂，也可以用作二次电池的电解质使用。
本发明还包括上述固态电解质材料在制备二次电池中的应用。采用本发明所述固态电解质材料可以改善电极离子传输速度，并与现有二次电池电极材料相兼容。
本发明还提供一种二次电池，该电池包括正极(层)，负极(层)，以及在所述正极(层)和负极(层)之间的电解质层；所述正极(层)、负极(层)和电解质层中至少一者含有一种或者多种上述固态电解质材料。
本发明中所述二次电池包括锂二次电池和钠二次电池。
本发明所述二次电池可按本领域常规方法进行制备。
本发明提供的固态电解质材料，在空气以及水相中稳定，不分解；其离子传导率可高于1mS cm -1；具有较宽的工作温度以及电化学惰性，电化学窗口达5伏以上，对氧化物正极稳定，在电池充放电过程中不分解，易于在二次电池中的应用。
本发明所提供的固态电解质材料成相温度较低，甚至于室温下球磨或者水相中干燥即可成相；其制备方法简单，易于大量制备应用。
卤化物电解质材料如Li 3YCl 6、Li 3InCl 6等材料与高压正极稳定，可以在干燥间中操作且材料偏软，易于成型加工，有望产业应用。然而，卤化物电解质材料普遍离子导较低，需要进一步提升其离子传导率。Li 3InCl 6电解质材料早在1992年被报道出来，其室温离子传导率仅有10 -5S/cm(Zeitschrift für anorganische und allgemeine Chemie 1992，613,26-30.)，还不能较好地满足锂二次电池的需要。
为此，本发明还提供一种锂离子传导率高的固态电解质材料。
本发明的发明人在实践中研究发现，通过对晶体结构中的原子排布调节可以提高锂离子传导率，从而获得了离子导>10 -3S/cm(室温)的铟基卤化物电解质材料。相对于前期报道的Li 3InCl 6电解质材料，经过结构调 节所得的铟基卤化物电解质Li 3b-3aIn aCl 3材料具有更高的离子传导率。而且本发明所得的固态电解质材料与商业常用的如LCO，NMC等氧化物正极材料相兼容，对空气稳定。有望解决全固态二次电池中卤化物固态电解质材料商业应用时所面临的离子传导率低的问题，还进一步有望解决现有制作工艺复杂以及价格昂贵等问题。另外，本发明进一步的还可以解决全固态二次电池中固态电解质材料化学以及电化学不稳定等问题。从而实现全固态二次电池的商业应用价值。
具体而言，本发明提供一种固态电解质材料，其具有Li 3b-3aIn aCl 3所示的组成，其中0.2≤a≤0.8，0.9≤b≤1.15；还具有第1晶相，该第1晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝14.6°±0.15°、16.7°±0.15°和34.3°±0.15°的位置具有峰。
根据本发明，在所述第1晶相中，所述原子排布与扭曲的LiCl晶体结构类似，Cl离子的排布与扭曲的LiCl晶体结构中的Cl离子排布类似。Li离子、空位以及铟离子排布在扭曲的LiCl晶体结构中的Li位。
根据本发明，在所述第1晶相中，所述铟离子与锂离子的占位不在同一位置。
根据本发明，在所述第1晶相中，所述空位排布具有两种类型，一种是与铟离子共位，另一种不与任何离子共位。
根据本发明，在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(131)面的X射线强度设为I (131)，此时，满足I (001)/I (131)>0.6。优选地，I (001)/I (131)>0.8。
根据本发明，在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(110)面的X射线强度设为I (110)，此时，满足I (110)/I (001)<0.85。优选地，I (110)/I (001)<0.65。
进一步地，本发明所述固态电解质材料还包含异种晶相，所述异种晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝10.8°±0.2°的位置具有峰。
根据本发明，所述异种晶相具有与所述第1晶相不同的晶体结构，且所述异种晶相介于所述第1晶相之间。
进一步地，本发明所述固态电解质材料还包含非晶相。
根据本发明，所述非晶相介于所述第1晶相之间。
根据本发明，所述固态电解质材料中，0.3≤a≤0.7，0.95≤b≤1.10；例如，具体地a可选0.53，b可选为1.03。
本发明所述固态电解质材料由于具有上述第1晶相，因而具有较高的离子传导率；特别是在进一步具有上述异种晶相及非晶相时，还可以与商业常用的如LCO，NMC等氧化物正极材料相兼容，对空气稳定。
通常而言，本发明所述固态电解质材料具有>10 -3S/cm的离子传导率(室温)。
在本发明一些实施方式中，所述固态电解质材料具有0.7-2.5mS/cm的离子传导率。
在本发明一些实施方式中，所述固态电解质材料具有1.0-2.0mS/cm的离子传导率。
在本发明一些具体实施方式中，所述固态电解质材料具有Li 1.5In 0.53Cl 3所示的组成，经检测，该材料在室温条件下离子传导率为2mS/cm。
在本发明一些实施方式中，所述固态电解质材料的X射线衍射(使用铜Kα射线测定)图如下文图24所示。
具体地，本发明所述固态电解质材料可采用水相法制备得到。采用的原料(或前驱物)包括锂源和铟源，其中锂源包括LiCl、Li 2CO 3、LiHCO 3、LiOH或醋酸锂；铟源包括InCl 3、InCl 3·4H 2O、In 2O 3、InOCl。
进一步地，所述水相法在制备过程中可以适当加入HCl、NH 4Cl等作为水解抑制剂或者配位剂。
进一步地，所述水相法具体包括：将所需原料或前驱物以一定的比例溶于水相中。
进一步地，所述水相法可将所需原料或前驱物在室温条件下溶于水相中，待全部组分溶解后，进行干燥即可获得所述固态电解质材料。所述干燥的温度通常为60-100℃，例如80℃，可在真空或非真空条件下进行干燥。例如可在在烘箱内进行干燥。干燥后的样品需在真空条件下进一步脱去结晶水，脱水温度为100～300℃，优选120～250℃。
进一步地，所述水相法中在脱水后可进一步进行退火处理，退火温度为300～600℃，优选350～550℃。其优点在于提高材料的结晶度，有利于 提高材料的稳定性以及离子传导率。
所述退火在空气气氛中进行，亦可在惰性气体气氛中或者真空气氛中进行。
进一步地，所述制备方法所述水相不仅可以使用去离子水，也可以改用有机溶剂或者是有机溶剂/水的混合溶剂进行扩展。
进一步地，所述制备方法所述有机溶剂为醇类，如乙醇。
本发明中还提供全固态锂电池，其具有正极活性物质层、负极活性物质层以及形成于上述正极活性物质层和上述负极活性物质层之间的固态电解质层，其中，上述正极活性物质层、上述负极活性物质层和上述固体电解质层中的至少一者含有上述的固态电解质材料。
根据本发明，通过使用上述的固态电解质材料，可制成输出特性高的全固态锂电池。进一步地，该全固态锂电池还具有较高的化学以及电化学稳定性。
本发明提供的固态电解质材料至少取得了锂离子传导率高的技术效果，进一步还取得了具有化学以及电化学稳定性的技术效果。
全固态二次电池相较于目前商用的液态二次电池具有更高的安全性和更高的能量密度。这是由于全固态二次电池采用了不可燃的固态快离子导体材料作为电解质。随着近几年的发展，目前已经开发出几种离子导高于1mS cm -1的固态电解质材料。特别是以Li 10Ge 2P 2S 12,Li 6PS 5Cl，Li 7P 3S 11以及Li 3PS 4为代表的硫化物固态电解质。然而，硫化物电解质对空气和水极其敏感，易于产生硫化氢等有毒气体，因此需要在惰性气体为保护气氛的环境下生产操作，从而增加了其生产成本、限制了其大规模生产应用能力；其次，硫化物电解质的电化学稳定窗口较窄(1.7～2.8V)，与氧化物电极材料(如LiCoO 2，NMC，Graphite等)会发生界面反应，因此界面修饰(电极材料表面包覆)在硫化物基全固态电池中变得不可或缺；另外，由于硫化物的化学不稳定性，易与极性溶剂反应，因而在制备浆料和电极涂布等电极过程中可以选择的溶剂和黏结剂是十分有限。由于以上诸多缺点，硫化物基全固态电池的大规模生产应用的能力非常有限。基于此进一步提出本发明。
本发明还提供一种电极(具体是一种基于卤化物固态电解质材料的电 极)及其制备方法。本发明还提供一种电解质薄层(具体是一种基于卤化物固态电解质材料的电解质薄层)及其制备方法。本发明还提供含所述电极或所述电解质薄层的电池。本发明通过固态电解质材料作为离子传导添加剂制备电极或电解质薄层，其显著的优点之一是无需惰性气氛即可生产操作，且制备所得电极和电解质层空气稳定。
特别地，本发明所述电极是指二次电池尤其是锂/锂离子二次电池(包括全固态电池和液相电池)中所用的电极。
本发明提供一种电极，其组分主要包括：固态电解质材料，电极材料，导电剂和黏结剂；
其中，所述固态电解质材料可选择具有Li aMX b所示的材料，其中M为Al、Ho、Ga、In、Sc、Y、La系中的一种或者几种，X为F、Cl、Br中的一种或者多种，0≤a≤10，1≤b≤13。
在本发明具体实施方式中，所述固态电解质材料可选自Li 3InCl 6、Li 3YCl 6、Li 3YBr 6、Li 3HoCl 6、Li 3ScCl 6等中的一种或几种。
其中，所述电极材料为正极材料或负极材料；进一步地，所述正极电极材料可以是LiCoO 2，NMC(镍钴锰三元锂离子氧化物材料)、LiFePO 4等传统氧化物正极材料，或者还可以是硫，硫化锂(Li 2S)，硫化聚丙烯腈等硫正极材料；所述负极材料可以是石墨，硅等负极材料。
其中，所述导电剂可为本领域的常规选择，例如导电炭黑，碳纳米管、乙炔黑，石墨烯等中的一种或几种。
其中，所述黏结剂可为本领域的常规选择，例如可以是水性黏结剂如丙烯腈多元共聚物的水分散液(LA 132，LA133等)、羧甲基纤维素钠(CMC)和丁苯橡胶(SBR)、海藻酸钠(SA)，也可以是油性黏结剂如聚偏氟乙烯(PVDF)、聚乙烯吡咯烷酮(PVP)等。
本发明所述电极还可包括本领域常用的其他功能性添加剂。
进一步地，本发明所述电极还包括集流体，具体可为本领域的常规选择。例如集流体可以选用铝箔(正极)、铝网(正极)、涂碳铝箔(正极)、碳纸(正负极)、不锈钢(正负极)、钛网(正负极)或者铜箔(负极)。
进一步地，本发明所提供的电极中电极材料的含量可以从50wt％到98wt％，优选为70wt％到95wt％；和/或，所述固态电解质材料的含量可以 从2wt％到50wt％，优选为5wt％到30wt％，和/或，所述导电剂的含量可以从1wt％到10％，和/或，所述黏结剂的含量可以从1wt％到10wt％。
进一步地，在制备本发明所提供的电极时除了直接加入所述所述固态电解质材料外，也可以直接加入其前驱体(例如LiCl，MCl 3)，在制浆过程中直接形成固态电解质材料。其中，制浆过程所用溶剂可以是水，也可以是乙醇，NMP，正庚烷等有机溶剂一种或几种；制备所得浆料可以在50-300℃进行真空干燥。浆料制备过程无需惰性气氛保护；也可以采用惰性气氛如氮气、Ar气。浆料制备过程可以在干燥间内进行也可以不在干燥间内进行。
进一步地，本发明所述电极材料可以是商业化的LiCoO 2，NMC等传统电极材料，无须额外的表面包覆。也可以是包覆的电极材料。
进一步地，本发明所提供的电极，所用电极材料可以无需经过特殊的表面包覆，也可以经过表面包覆层修饰，所述表面包覆层可以是经过ALD沉积得到的表面包覆，其中包含Li-Nb-O，Li-Ta-O，Li-P-O,Li-Si-O,Li-Ti-O；也可以是通过溶胶凝胶法合成得到的表面包覆材料，经过分子层沉积技术得到的表面包覆层，其中包含但不限于聚乙二醇铝(Alucone)，聚尿酸(ployurea)，聚3,4-乙烯二氧噻吩(PEDOT)；还可以是经过溶胶凝胶法合成的表面包覆层，其中包括但不限于，Li-Nb-O，Li-Ta-O，Li-Nb-Ta-O。
在本发明一些具体实施方式中，所述电极材料包覆于所述固态电解质材料中；其中，所述电极材料与所述固态电解质材料的重量比为95:5，90:10,85:15,80:20,70:30,更优选为85:15。研究发现，本发明所提供的电极将所述电极材料包覆于所述固态电解质材料中的优点在于改善了固态电解质与电极之间的固固接触，提高了固态电池中电极活性材料的利用率，降低了电极中固态电极中电解质的含量，从而提高了全固态电池的能量密度。
本发明中将所述电极材料包覆于所述固态电解质材料中形成复合电极材料的制备方法如下：
将所述固态电解质材料或其前躯体溶于水中，再加入所述电极材料，混匀，干燥(例如在100℃条件下进行干燥)，然后再进一步真空脱水干燥(例如在200℃条件下)，即可。或者制备方法如下：
将所述固态电解质材料或其前躯体，以及电极材料溶于有机溶剂中， 超声分散，干燥(例如在100℃条件下进行干燥)，然后再进一步真空脱溶剂干燥(例如在200℃条件下；例如时间为5小时左右)，即可。
本发明所提供的电极可采用本领域常规方法制备。在其制备方法中，通常在整个制备过程无需惰性气氛保护，便于实际生产操作。而现有的硫化物电解质必须在惰性气氛下进行操作生产。
本发明还可以直接从前驱体开始，在电极材料上直接原位包覆卤化物电解质材料。而硫化物电解质是在苛刻的条件下合成出固态电解质，然后在分散与电极中。相比而言，本发明所提出的原位包覆的方法更加简单方便，且提高了电极材料与电解质之间的固固接触。
另外，本发明所提供的电极的优点在于所述固态电解质材料与电解质具有良好的固固接触，活性材料利用率接近100％，电极中固态电解质的含量较少(<15％)(目前文献中报道的固态电极中固态电解质含量将近30％)，在全固态电池的电极中，减少固态电解质的含量会显著增加电池能量密度。
另外，本发明所提供的电极可根据需要制成本领域常规形状或形态。
本发明还提供一种电解质薄层，主要包括固态电解质材料和黏结剂；其中所述固态电解质材料和黏结剂可与上文含义相同。在其制备过程中所用的溶剂也可以与上文相同。
本发明提供的电解质薄层的突出优点在于其厚度小，通常其厚度可小于50微米。在本发明一些具体实施方式中，所提供的电解质薄层的厚度为20～200微米。
由于本发明所述电解质薄层具有较低的厚度，将其用于固态电池中可以显著提高全固态电池的能量密度。
本发明所述电解质薄层可采用本领域常规方法制备；制备过程无需惰性气氛保护。可以采用水相或有机相为溶剂以及胶黏剂来实现该电解质薄层的制备。
在本发明一些具体实施方式中，所述电解质薄层制备方法如下：
将黏结剂溶于溶剂中，再加入所述固态电解质材料或其前躯体(例如LiCl，MCl 3)和导电剂制成浆料(可通过调节溶剂的量来调配浆料的浓度)，然后涂布在集流体或柔性基底上，干燥(例如在100-110℃调节下真空干 燥)，再从所述集流体或柔性基底上剥离，即可。
进一步地，所述集流体可以是铜箔；所述柔性基底可以是镍网，PEO薄膜等。
进一步地，在本发明所提供的电解质薄层中，所述固态电解质材料的含量可以从20wt％到100wt％，优选45wt％到99wt％；黏结剂的含量可以从0到80wt％，优选1wt％到55wt％；
进一步地，本发明所提供的电解质薄层可以采用柔性基底，比如PEO薄膜，glass fiber等作为自支撑的薄膜。
本发明还包括如上所述的固态电解质材料在制备电极或电解质薄层中的应用。
本发明提供的固态电解质材料可在水溶液中进行合成。目前还没有关于固态电解质可以在水相中合成的报道。本发明可以采用水系黏结剂，水作为溶剂来合成固态电解质，也可以用水来制作固态电极和固态电解质层。成本低且环保。
在本发明一些实施例中，上述电极或上述电解质薄层中所用的固态电解质材料也可以是上述具有Li 3b-3aIn aCl 3所示组成的固态电解质材料，其中0.2≤a≤0.8，0.9≤b≤1.15；还具有第1晶相，该第1晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝14.6°±0.15°、16.7°±0.15°和34.3°±0.15°的位置具有峰。关于所述Li 3b-3aIn aCl 3所示组成的固态电解质材料，具体可参见上文以及下文实施例和附图。
本发明还包括上述电极或上述电解质薄层在制备电池尤其是二次电池特别是锂/锂离子二次电池(包括全固态电池和液相电池)中的应用。
本发明还提供一种二次电池特别是锂/锂离子二次电池(包括全固态电池和液相电池)，其包括上述电极或包括上述电解质薄层；还包括二次电池的其他常规组件。
本发明提供的电极、电解质薄层具有如下优势：
(1)可以用水作为溶剂涂布电极；
(2)离子导可达1.5×10 -3S/cm以上，
(3)生产操作无需惰性气氛保护，降低了生产成本，工艺简单；
(4)所得电极具有一定的机械柔性；
(5)与现在的锂离子电池生产过程十分兼容；
(6)可以在电极材料上原位合成固态电解质(一步法)，形成固态电解质包覆电极材料的结构，从而改善了电极与固态电解质之间的固固接触，提高了全固态电池中活性材料的利用率，降低了固态电极中固态电解质的含量，从而提高了固态电池的能量密度。
本发明采用一种空气稳定的、高离子传导的、且易宏量制备的固态电解质材料作为全固态电池的离子传导的添加剂；且由于固态电解质材料与氧化物电极材料(如LCO,NMC等)的兼容性，传统的正极材料无需做额外的界面修饰。在电极和电解质的制造过程中，无需惰性气氛保护、且与传统的电极制造技术十分兼容、工艺简单、成本低，极具大规模生产能力，从而极具商业应用价值。
附图说明
图1是实施例1.1中玻璃-陶瓷相Li 3Y 1-dIn dCl 6(d＝0.2)添加剂的X射线衍射图；
图2是实施例1.1中玻璃-陶瓷相Li 3Y 1-dIn dCl 6(d＝0.2)添加剂的变温离子电导率图；
图3是实施例1.1中玻璃-陶瓷相Li 3Y 1-dIn dCl 6添加剂d的取值与相应产物离子导变化曲线。
图4是实施例1.2中结晶相Li 3InCl 6的X射线衍射图；
图5是实施例1.2中结晶相Li 3InCl 6的变温离子电导率图；
图6是应用例1.1中全固态的LiIn-LiCoO 2二次电池的充放电曲线。
图7是应用例1.1全固态的LiIn-NMC811二次电池的充放电曲线。
图8是应用例1.2液相Li-LCO二次电池的充放电曲线；
图9是实施例2.1在水溶液中获得的z＝1/7(Li 4InCl 7)的X射线衍射图；
图10是实施例2.1在水溶液中获得的Li 4InCl 7的变温离子电导率图；
图11是实施例2.2在水溶液中获得的Li 3InCl 5F的变温离子电导率图；
图12是实施例2.3中获得的Li 1-3zIn zCl(0.1≤z≤0.25)的室温离子电导率随z变化关系图；
图13是实施例2.5中获得的玻璃-陶瓷相Li 3In 0.8Y 0.2Cl 6固态电解质材料的X射线衍射图；
图14是实施例2.5中获得的玻璃-陶瓷相Li 3In 0.8Y 0.2Cl 6固态电解质材料的变温离子电导率图；
图15是实施例2.6中获得的玻璃-陶瓷相Li 2In 0.1Zn 0.9Cl 4.1固态电解质材料的X射线衍射图；
图16是实施例2.7中获得的玻璃-陶瓷相LiGaCl 4固态电解质材料的X射线衍射图；
图17是实施例2.7中获得的玻璃-陶瓷相LiGaCl 4固态电解质材料在室温条件下的阻抗曲线；
图18是实施例2.8中获得的玻璃-陶瓷相Li 6FeCl 8固态电解质材料的X射线衍射图；
图19是实施例2.8中获得的玻璃-陶瓷相Li 6FeCl 8固态电解质材料在室温条件下的阻抗曲线；
图20是实施例2.9中获得的玻璃-陶瓷相Li 3YCl 6固态电解质材料的X射线衍射图；
图21是实施例2.9中获得的玻璃-陶瓷相Li 3YCl 6固态电解质材料的变温离子电导率图；
图22是应用例2.1中全固态的LiIn-LiCoO 2二次电池的充放电曲线。
图23是应用例2.1全固态的LiIn-NMC811二次电池的充放电曲线；
图24是实施例3.1中获得的Li 1.5In 0.53Cl 3固态电解质材料的X射线衍射及其相应的结构精修图；
图25是实施例3.1中获得的Li 1.5In 0.53Cl 3固态电解质材料同步辐射X射线吸收光谱图及其拟合结构模型；
图26是实施例3.1中获得的Li 1.5In 0.53Cl 3固态电解质材料的晶体结构及其原子分布图；
图27是实施例3.1中获得的Li 1.5In 0.53Cl 3固态电解质材料电化学表征。a为该材料的变温阻抗曲线及其对应的离子传导率，b为该材料电压窗口测试曲线；
图28是应用例3.1中全固态的LiIn-LiCoO 2二次电池的充放电曲线；
图29是应用例3.1全固态的LiIn-NMC811二次电池的充放电曲线；
图30表示实施例4.1水相形成Li 3InCl 6包覆的LiCoO 2正极材料的过 程及所制备的材料；
图31表示实施例4.2水相原位形成Li 3InCl 6包覆的LiCoO 2正极材料的过程及所制备的材料；
图32表示实施例4.3有机相形成Li 3InCl 6包覆的NMC532正极材料的过程及所制备的材料；
图33表示实施例4.4有机相原位形成Li 3InCl 6包覆的NMC532正极材料的过程及所制备的材料；
图34表示实施例4.5制备有机相涂布电极材料的过程及所制备的材料；
图35表示实施例4.6制备有机相涂布电解质层的过程及所制备的材料。
具体实施方式
以下实施例用于说明本发明，但不用来限制本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购买得到的常规产品。
以下实施例中，研磨在手套箱内进行，手动研磨或机器研磨均可；球磨操作可在氧化锆球磨罐内进行，通常是密封球磨。
实施例1.1 玻璃-陶瓷相Li 3Y 1-dIn dCl 6添加剂及其制备
把30毫摩尔的LiCl(1.29克)、10-10a毫摩尔的InCl 3以及10a毫摩尔的YCl 3研磨后置于氧化锆球磨罐内，球料比为30:1，随后密封球磨30小时，球磨转速为550转每分钟。球磨后所得样品即为玻璃-陶瓷相Li 3Y 1-dIn dCl 6添加剂。其中，d为0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9和1.0。
图1、图2分别为本实施例制得的玻璃-陶瓷相Li 3Y 1-dIn dCl 6(d＝0.2)的X射线衍射图、变温离子电导率图。图3为d的上述取值与相应产物离子导变化曲线。
实施例1.2 结晶相Li 3InCl 6添加剂及其制备
把30毫摩尔的LiCl(1.29克)，10毫摩尔的InCl 3(2.21克)研磨后置于氧化锆球磨罐内，球料比为20:1，随后密封球磨20小时，球磨转速为550转每分钟。球磨后所得中间产物在密封石英管内450℃反应10小时。所得产物即为结晶相Li 3InCl 6添加剂。
图4、图5分别为本实施例制得的结晶相Li 3InCl 6的X射线衍射图、变温离子电导率图。
实施例1.3 玻璃相Li 3NbCl 8添加剂及其制备
制备方法与实施例1.1类似，区别仅在于：所用原料如下：30毫摩尔的LiCl(1.29克)和2.7克的NbCl 5；球磨转速改为450转每分钟，球磨时间为10小时。前驱物经球磨后即可获得玻璃相Li 3NbCl 8添加剂。
实施例1.4 玻璃-陶瓷相Li 3YCl 6电极添加剂材料及其制备
把30毫摩尔的LiCl(1.29克)，10毫摩尔的YCl 3(1.95克)、20毫摩尔的氯化铵(1.08克)研磨混合后溶于四氢呋喃溶剂中。随后把所得溶液置于真空干燥箱内150℃下烘干。所得中间产物经氩气气氛下煅烧500℃5小时后即可获得玻璃-陶瓷相Li 3YCl 6电极添加剂材料。
应用例1.1 实施例1.2制备的结晶相Li 3InCl 6电极添加剂材料在全固态LiIn-LiCoO 2、LiIn-LiNi 0.8Mn 0.1Co 0.1O 2(LiIn-NMC811)中的应用
采用不经修饰的LiCoO 2以及NMC811为正极材料。以正极材料：结晶相Li 3InCl 6电极添加剂材料为70:30(质量比)的配比进行混合，混合过程在手套箱内进行，具体的过程是采用研钵研磨20分钟。研磨后的材料作为正极粉体。以金属薄铟片作为负极，电解质同样采用商业的Li 10GeP 2S 12电解质材料。取100毫克Li 10GeP 2S 12电解质材料放入横截面面积为0.785平方厘米的模具电池内胆中，以200兆帕的压强进行压片获得电解质层。随后，在电解质层一边加入10毫克的正极粉体，铺匀后以350兆帕的压强进行第二次压片，把正极层压与电解质层压到一块。随后在另一边放入铟片作为负极层。整个过程完成后，把内胆放入模具电池中，压紧并拧紧螺丝进行密封。密封后即可获得全固态的LiIn-LiCoO 2和LiIn-NMC811二次电池。其中全固态的LiIn-LiCoO 2电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.6伏。图6为该电池的1-5圈的充放电曲线图，首圈充电容量142毫安时每克钴酸锂，首圈放电容量为131毫安时每克钴酸锂，对应的首圈库伦效率为91.7％。随后电池容量稳定在130毫安时每克钴酸锂左右，电池循环的可逆性较好。其中全固态的LiIn-NMC811电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.9伏。图7为该电池的首圈的充放电曲线图，首圈充电容量231毫安 时每克NMC811，首圈放电容量为192毫安时每克NMC811，对应的首圈库伦效率为83.1％。
应用例1.2 实施例1.2制备的结晶相Li 3InCl 6电极添加剂材料在液相Li-LiCoO 2中的应用
采用不经修饰的LiCoO 2为正极材料。以正极材料：结晶相Li 3InCl 6电极添加剂材料为90:10(质量比)的配比进行混合，混合过程在手套箱内进行，具体的过程是采用研钵研磨20分钟。研磨后的材料作为正极粉体。采用85wt％正极粉体、10wt％PVDF胶黏剂以及5wt％导电炭黑进行搅拌制浆，制浆的溶剂采用NMP。所获得浆料涂布于金属铝箔上。经真空100℃烘干即可获得正极片。极片厚度大于400微米，单面LCO的负载高于20毫克每平方厘米。以锂片为对电极，聚烯烃多孔膜(Celgard 2500)为隔膜，以LiPF 6的碳酸乙烯酯(EC)和碳酸二甲酯(DMC)(体积比1:1)的混合溶液作为电解液，CR2016电池组装在氩气气氛的手套箱中完成。在测试温度为25℃下进行电性能测试。图8为该电池的首圈的充放电曲线图，首圈充电容量139毫安时每克LCO，首圈放电容量为129毫安时每克LCO，对应的首圈库伦效率为92.8％。
以上实验结果表明，本发明提供锂二次电池添加剂可以改善电极离子传输速度，并与现有锂二次电池电极材料相兼容。该材料室温离子传导率较高，空气稳定，同时制备方法简单，并与现有锂二次电池电极材料相兼容。有望解决锂二次电池中电极材料离子传输较慢、电极材料负载低，电极厚度难以进一步提高等方面的问题，从而有望实现具有高能量密度以及低电极极化的电极极片的制备，进一步提高锂二次电池的能量密度。
实施例2.1 在水溶液中制备Li 4InCl 7固态电解质材料
把40毫摩尔的LiCl(1.7克)、10毫摩尔的InCl 3(2.21克)在空气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入10毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于烘箱内90℃进行干燥，干燥后所获得的样品进一步的放置于260℃的马弗炉内进行退火。退化时间为5个小时。经退火后所获得的样品即为玻璃-陶瓷相Li 4InCl 7固态电解质材料。
图9、图10分别为本实施例制备的玻璃-陶瓷相Li 4InCl 7固态电解质材 料的X射线衍射图和变温离子电导率图。
实施例2.2 在水溶液中制备Li 3InCl 5F固态电解质材料
与实施例2.1类似，所不同的是40毫摩尔的LiCl(1.7克)前驱物改成20毫摩尔的氯化锂(0.85克)和10毫摩尔的氟化锂(0.26克)混合物。退火温度改为400℃。退火后所获得的样品为玻璃-陶瓷相Li 3InCl 5F固态电解质材料。
图11为本实施例制备的玻璃-陶瓷相Li 3InCl 5F固态电解质材料的变温离子电导率图。
实施例2.3 水相环境下制备多种Li 1-3zIn zCl(z＝0.25,0.2,0.167,0.143,0.1)固态电解质材料。
把LiCl和InCl 3按照1-3z：z(z＝0.25,0.2,0.167,0.143,0.1)的比例进行混合，同时保证LiCl和InCl 3的投料为40毫摩尔。随后加入5毫升的去离子水进行溶解。待全部前驱物溶解完全后，置于干燥箱内100℃进行干燥。干燥后所获得的样品即为玻璃-陶瓷相Li 1-3zIn zCl(0.1≤z≤0.25)固态电解质材料。
图12是本实施例制备的玻璃-陶瓷相Li 1-3zIn zCl(0.1≤z≤0.25)固态电解质材料室温离子传导率与z的关系曲线图。
实施例2.4 玻璃-陶瓷相Na 3InCl 4Br 2固态电解质材料的制备
把10毫摩尔的NaCl(0.58克)，10毫摩尔的NaBr(1.03克)和10毫摩尔的InCl 3(2.21克)在空气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入7毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于烘箱内90℃进行干燥，干燥后所获得的样品进一步的放置于350℃的马弗炉内进行退火。退化时间为5个小时，退火气氛为真空环境。经退火后所获得的样品即为玻璃-陶瓷相Na 3InCl 4Br 2固态电解质材料。
实施例2.5 玻璃-陶瓷相Li 3In 0.8Y 0.2Cl 6固态电解质材料的制备
把30毫摩尔的LiCl(1.272克)、8毫摩尔的InCl 3(1.768克)、2毫摩尔的YCl 3(0.39克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入10毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于烘箱内90℃进行干燥，干燥后所获得的样品进一步的放置于200℃的真空干燥箱中进行反应。反应后所得产物密封于石英玻璃 管内，并置于马弗炉内进行退火，退火温度为500℃，退火时间为8小时。经退火后所获得的样品即为玻璃-陶瓷相Li 3In 0.8Y 0.2Cl 6固态电解质材料。
图13、图14分别为本实施例制备的玻璃-陶瓷相Li 3In 0.8Y 0.2Cl 6固态电解质材料的X射线衍射图和变温离子电导率图。
实施例2.6 玻璃-陶瓷相Li 2In 0.1Zn 0.9Cl 4.1固态电解质材料的制备
把20毫摩尔的LiCl(0.848克)、9毫摩尔的ZnCl 2(1.224克)和1毫摩尔的InCl3(0.221克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入5毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于通风橱内的加热板上90℃进行干燥，干燥后所获得的样品进一步放置于200℃的真空干燥箱中反应5小时。随后在真空气氛下300℃退火，退火时间为60分钟，所获得的样品即为玻璃-陶瓷相Li 2In 0.1Zn 0.9Cl 4.1固态电解质材料。
图15为本实施例制备的玻璃-陶瓷相Li 2In 0.1Zn 0.9Cl 4.1固态电解质材料的X射线衍射图。
实施例2.7 玻璃-陶瓷相LiGaCl 4固态电解质材料的制备
把10毫摩尔的LiCl(0.424克)、10毫摩尔的GaCl 3(1.76克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入3毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于通风橱内的加热板上90℃进行干燥，干燥后所获得的样品进一步放置于200℃的真空干燥箱中反应5小时。所获得的样品即为玻璃-陶瓷相LiGaCl 4固态电解质材料。
图16、图17分别为本实施例制备的玻璃-陶瓷相LiGaCl 4固态电解质材料的X射线衍射图和室温条件下的阻抗曲线。从图17上可以计算得到该材料的室温离子传导率为9*10 -5S/cm。
实施例2.8 玻璃-陶瓷相Li 6FeCl 8固态电解质材料的制备
把30毫摩尔的LiCl(1.272克)、5毫摩尔的FeCl 2(0.634克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入5毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于真空箱内90℃进行真空干燥，干燥后所获得的样品进一步在200℃下脱水5小时。所获得的样品即为玻璃-陶瓷相Li 6FeCl 8固态电解质材料。
图18、图19分别为本实施例制备的玻璃-陶瓷相Li 6FeCl 8固态电解质材料的X射线衍射图和室温条件下的阻抗曲线。从图19上可以计算得到该材料的室温离子传导率为5*10 -6S/cm。
实施例2.9 玻璃-陶瓷相Li 3YCl 6固态电解质材料的制备
把30毫摩尔的LiCl(1.272克)、10毫摩尔的YCl 3(1.953克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入5毫升的无水乙醇进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于氩气内90℃进行干燥，干燥后所获得的样品进一步在200℃下脱水5小时，随后采用500℃退火2个小时。所获得的样品即为玻璃-陶瓷相Li 3YCl 6固态电解质材料。
图20、图21分别为本实施例制备的玻璃-陶瓷相Li 3YCl 6固态电解质材料的X射线衍射图和变温离子电导率图。
实施例2.10 玻璃-陶瓷相Li 3BiCl 6固态电解质材料的制备
把30毫摩尔的LiCl(1.272克)、10毫摩尔的BiCl 3(3.15克)在氩气气氛下称取并且转移到20毫升的玻璃瓶内，随后加入10毫升的浓盐酸进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于通风橱内的加热板上90℃进行干燥，干燥后所获得的样品进一步放置于200℃的真空干燥箱中反应5小时。所获得的样品即为玻璃-陶瓷相Li 3BiCl 6固态电解质材料。
应用例2.1：实施例2.1制备的玻璃-陶瓷相Li 4InCl 7固态电解质材料在全固态LiIn-LiCoO 2、LiIn-LiNi 0.8Mn 0.1Co 0.1O 2(LiIn-NMC811)中的应用。
采用不经修饰的LiCoO 2以及NMC811为正极材料。以正极材料：实施例2.1所获得的玻璃-陶瓷相Li 4InCl 7固态电解质材料为90:10(质量比)的配比进行混合，混合方式采用手动研磨的形式研磨5分钟，混合过程采用在空气气氛中进行，研磨后的样品置于20毫升玻璃仪器瓶内，加入样品五倍质量的去离子水进行分散，随后置于超声仪器中超声5分钟。超声结束后，把该玻璃仪器瓶置于真空干燥箱内在真空环境下80℃干燥12小时。干燥后所得样品即为二次电池正极粉体。以金属薄铟片作为负极，电解质同样采用玻璃-陶瓷相Li 4InCl 7固态电解质材料以及商业的Li 10GeP 2S 12电解质材料。取50毫克Li 4InCl 7固态电解质材料放入横截面面积为0.785 平方厘米的模具电池内胆中，以100兆帕的压强进行压片获得第一层电解质层。随后取50毫克Li 10GeP 2S 12电解质材料置于第一层电解质层的一端，以200兆帕的压强进行压片获得双层的电解质层。随后，在Li 4InCl 7电解质层那端加入10毫克的正极粉体，铺匀后以350兆帕的压强进行第三次压片，把正极层压与电解质层压到一块。随后在Li 10GeP 2S 12电解质材料那一端放入铟片作为负极层。整个过程完成后，把内胆放入模具电池中，压紧并拧紧螺丝进行密封。密封后即可获得全固态的LiIn-LiCoO 2和LiIn-NMC811二次电池。其中全固态的LiIn-LiCoO 2电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.6伏。图22为该电池的充放电曲线图。其中全固态的LiIn-NMC811电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.9伏。图23为该电池的首圈的充放电曲线图。
应用例2.2：实施例2.4制备的玻璃-陶瓷相Na 3InCl 4Br 2固态电解质材料在全固态钠二次电池中的应用
采用不经修饰的NaCrO 2为正极材料。以正极材料：玻璃-陶瓷相Na 3InCl 4Br 2固态电解质材料:导电炭黑为80:15:5(质量比)的配比进行混合，混合过程在手套箱内进行，具体的过程是采用研钵研磨20分钟。研磨后的材料作为正极粉体。以锡片为负极，玻璃-陶瓷相Na 3InCl 4Br 2固态电解质材料为电解质。取100毫克Na 3InCl 4Br 2固态电解质材料放入横截面面积为0.785平方厘米的模具电池内胆中，以100兆帕的压强进行压片获得电解质层。随后，在电解质层一端加入10毫克的正极粉体，铺匀后以350兆帕的压强进行第二次压片，把正极层压与电解质层压到一块。随后在电解质层另一端放入锡片作为负极层。整个过程完成后，把内胆放入模具电池中，压紧并拧紧螺丝进行密封。密封后即可获得全固态的NaCrO 2/Sn二次电池。在测试温度为25℃下进行电性能测试。
以下X射线衍射均为使用铜Kα射线测定。
以下离子传导率的方法采用交流阻抗进行测试，测试方法为：在手套箱内称取150毫克的电解质材料，随后在模具电池内压片，压力为350MPa，然后量取电解质层的厚度记为L，随后在模具电池内直接组装成碳/电解质/碳的对称电池，测量该电池在开路条件下的交流阻抗，所得阻抗值记为R， 利用公式σ＝L/(R·A)进行计算，其中σ为离子传导率，L为电解质层的厚度，R为阻抗值，A为电解质片的电极面积。
实施例3.1 Li 3b-3aIn aCl 3(a＝0.53,b＝1.03)固态电解质材料的制备
把30毫摩尔的LiCl(1.275克)、10毫摩尔的InCl 3·4H 2O(2.93克)在空气气氛下称取并且转移到100毫升的玻璃瓶内，随后加入20毫升的去离子水进行溶解混合。待所有材料都完全溶解后，把该玻璃瓶置于烘箱内80℃进行真空干燥，干燥后所获得的样品于200℃的真空烘箱内进行进一步的脱水。脱水时间为5个小时。经脱水后所获得的样品即为玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料。
图24为本实施例制备的玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料的X射线衍射及其相应的结构精修图；
图25为本实施例制备的玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料同步辐射X射线吸收光谱图及其拟合结构模型。
从以上X射线衍射及其相应的结构精修以及同步辐射X射线吸收光谱图分析显示，本实施例所获得的Li 1.5In 0.53Cl 3固态电解质材料晶体结构中铟离子具有与文献以及数据库中报道不同的排布方式。
无机晶体结构数据库(卡片号04-009-9027)中的Li 3InCl 6晶体结构，铟离子排布在In 1(0,0.333,0)以及In 2(0,0,0)两个位置，In 1位置上铟离子占比7％，In 2位置上铟离子占比87.5％，具体见下表1。
表1 Li 3InCl 6晶体结构的原子排布
原子 x y z 占位 位置
Cl1 0.2421 0.1622 0.2388 1.000 8j
Cl2 0.2450 0.0000 -0.2338 1.000 4i
In1 0.0000 0.3333 0.0000 0.07 4g
In2 0.0000 0.0000 0.0000 0.875 2a
Li1 0.5000 0.0000 0.5000 1.000 2d
Li2 0.0000 0.1683 0.5000 1.000 4h
本实施例所制备的Li 1.5In 0.53Cl 3固态电解质材料其铟离子全部排布在In 1(0,0.333,0)位置上，占比53％，具体见下表2。
表2 实施例3.1制备的Li 1.5In 0.53Cl 3固态电解质材料的晶体结构及其 原子分布
原子 x y z 占位 位置
Cl1 0.2421 0.1622 0.2388 1.000 8j
Cl2 0.2450 0.0000 -0.2338 1.000 4i
In1 0.0000 0.3333 0.0000 0.530 4g
Li1 0.5000 0.0000 0.5000 1.000 2d
Li2 0.0000 0.1683 0.5000 1.000 4h
图26为本实施例所制备的Li 1.5In 0.53Cl 3固态电解质材料晶体结构及其原子分布图；
图27a为本实施例所制备的Li 1.5In 0.53Cl 3固态电解质材料的变温阻抗曲线及其对应的离子传导率。该材料在室温条件下离子传导率为2mS/cm；图27b为本实施例所制备的Li 1.5In 0.53Cl 3固态电解质材料电压窗口测试曲线，该测试方法采用Li/电解质/Au电池以循环伏安的测试方法进行。
应用例3.1：实施例3.1制备的玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料在全固态LiIn-LiCoO 2、LiIn-LiNi 0.8Mn 0.1Co 0.1O 2(LiIn-NMC811)中的应用。
采用不经修饰的LiCoO 2以及NMC811为正极材料。以正极材料：实施例3.1所获得的玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料为70:30(质量比)的配比进行混合，混合方式采用手动研磨的形式研磨5分钟，混合过程采用在手套箱内进行，所得样品即为二次电池正极粉体。以金属薄铟片作为负极，电解质同样分别采用实施例3.1所获得玻璃-陶瓷相Li 1.5In 0.53Cl 3固态电解质材料以及商业的Li 10GeP 2S 12电解质材料。取50毫克Li 1.5In 0.53Cl 3固态电解质材料放入横截面面积为0.785平方厘米的模具电池内胆中，以100兆帕的压强进行压片获得第一层电解质层。随后取50毫克Li 10GeP 2S 12电解质材料置于第一层电解质层的一端，以200兆帕的压强进行压片获得双层的电解质层。随后，在Li 1.5In 0.53Cl 3电解质层那端加入10毫克的正极粉体，铺匀后以350兆帕的压强进行第三次压片，把正极层压与电解质层压到一块。随后在Li 10GeP 2S 12电解质材料那一端放入铟片作 为负极层。整个过程完成后，把内胆放入模具电池中，压紧并拧紧螺丝进行密封。密封后即可获得全固态的LiIn-LiCoO 2和LiIn-NMC811二次电池。其中全固态的LiIn-LiCoO 2电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.6伏。图28为全固态的LiIn-LiCoO 2电池的充放电曲线图。其中全固态的LiIn-NMC811电池采用100微安的电流密度进行充放电测试，截止电压为1.9-3.8伏。图29为全固态的LiIn-NMC811电池的首圈的充放电曲线图。
结果表明，实施例3.1制备的Li 1.5In 0.53Cl 3固态电解质材料与无机晶体结构数据库(卡片号04-009-9027)中Li 3InCl 6晶体结构的离子排布位置不同，并且该电解质材料具有更高的离子传导率，从而实现该材料在固态电池中的应用。
附图中涉及的英文具体的中文含义见表3
表3 附图中英文对照
英文 中文
ExpData 实验数据
Normalized 归一化的数据
Photon Energy 光子能量
Modeling 模型拟合
Normalized Absorption 归一化的吸收强度
arb unit 吸收能量
Current 电流
Voltage 电压
Solid electrolyte 固态电解质
Capacity 容量
实施例4.1 水相形成Li 3InCl 6包覆的LiCoO 2正极材料
将75mg的Li 3InCl 6溶解在2g的水中，然后再加入425mg的LiCoO 2，置于100℃干燥，再转移至200℃真空烘箱中进一步脱水干燥，得到L i3InCl 6包覆的LiCoO 2；整个实验过程无需惰性气氛保护。
图30中，(a)表示具体合成过程；Heating表示加热，Vacuum表示真空条件；(b,c)表示包覆前LiCoO 2的SEM照片；(d,e)表示包覆后 LiCoO 2的SEM照片。
实施例4.2 水相原位形成Li 3InCl 6包覆的LiCoO 2正极材料
将27.4mg的LiCl和47.6mg的InCl 3溶解在水中，再加入425mg的LiCoO 2，置于100度烘箱蒸干，再转移至200度真空烘箱中反应5小时。得到Li 3InCl 6包覆的LiCoO 2，(Li 3InCl 6与LiCoO 2的质量比为15:85)。整个实验过程无需惰性气氛保护。
图31中，(a)表示具体合成过程；Heating表示加热，Vacuum表示真空条件；(b)包覆前LiCoO 2的SEM照片；(c,d)包覆后LiCoO 2的SEM照片；(e)包覆不同含量Li 3InCl 6的LiCoO 2的首次充放电曲线；(f)包覆不同含量Li 3InCl 6的LiCoO 2的循环稳定性。(e)的横坐标表示放电比容量，纵坐标表示对金属锂负极的电压；恒流充放电的电流密度为0.13mA/cm 2.。(f)横坐标表示循环圈数，左侧纵坐标表示放电比容量，右侧纵坐标表示库伦效率，循环测试的电流密度为0.13mA/cm 2。(e)和(f)中实验样品为按照上述方法控制的合成了不同质量比(05：95,10:10，15:85)的Li 3InCl 6包覆的LiCoO 2电极。电化学测试结果显示，含有15％的Li 3InCl 6的LiCoO 2电极首次放电比容量为131mAh/g.60圈循环之后保持在106.4mAh/g.含有10％的Li 3InCl 6的LiCoO 2电极首次放电比容量为91.6mAh/g.60圈循环之后保持在64.7mAh/g.含有5％的Li 3InCl 6的LiCoO 2电极首次放电比容量为40.1mAh/g.60圈循环之后保持在12.9mAh/g。
实施例4.3 有机相形成Li 3InCl 6包覆的NMC532正极材料
将75mg的Li 3InCl 6和425mg的NMC532至于2g乙醇中，超声分散5分钟，然后转移至100度烘箱中干燥，再转移至200度真空烘箱中进一步脱溶剂干燥。得到Li 3InCl 6包覆的NMC532(NMC532与Li 3InCl 6的质量比为85:15)，整个实验过程无需惰性气氛保护。
按基本相同的方法分别控制NMC532与Li 3InCl 6的质量比为80:20、90:10，制备包覆不同含量Li 3InCl 6的NMC532。
图32中，(a)表示具体合成过程；Ethanol表示乙醇，Heating表示加热，Vacuum表示真空条件；(b)表示包覆不同含量Li 3InCl 6的NMC532的电镜照片。
实施例4.4 有机相原位形成Li 3InCl 6包覆的NMC532正极材料
将3摩尔LiCl和1摩尔InCl 3(总质量为150mg)溶解在2克乙醇中，再加入850毫克的SC-NMC532(单晶NMC532)，置于100度烘箱蒸干，再转移至200度真空烘箱中反应5小时，得到Li 3InCl 6包覆的SC-NMC532，(Li 3InCl 6与SC-NMC532的质量比为15:85)。整个实验过程无需惰性气氛保护。SC表示单晶。
图33中，(a)表示具体合成过程；Ethanol表示乙醇，Heating表示加热，Vacuum表示真空条件；(b)包覆前SC-NMC532的SEM照片；(c,d)包覆后SC-NMC532的SEM照片；(e)包覆不同含量Li 3InCl 6的LiCoO 2的首次充放电曲线；(f)包覆不同含量Li 3InCl 6的LiCoO 2的循环稳定性。(e)的横坐标表示放电比容量，纵坐标表示对金属锂负极的电压。恒流充放电的电流密度为0.13mA/cm 2。(f)横坐标表示循环圈数，左侧纵坐标表示放电比容量，右侧纵坐标表示库伦效率，循环测试的电流密度为0.13mA/cm 2。(e)和(f)中实验样品为按照上述方法控制的合成的Li 3InCl 6包覆的SC-NMC532电极，其中Li 3InCl 6和SC-NMC532的质量比为15％:85wt％.其中SC表示单晶。电化学测试结果表明：SC-NMC532在Li 3InCl 6的电解质中首次放电比容量高达159mAh/g，经过10圈循环之后，克容量保持在137.6mAh/g。
实施例4.5 有机相涂布电极材料
先将100毫克的PVDF溶解在一定质量的NMP中，再称取150毫克的Li 3InCl 6，850毫克的LiCoO 2，和100毫克的乙炔黑加入PVDF-NMP的溶液中，通过调节添加NMP的含量配成浆料，然后刮涂在涂碳铝箔集流体上，再转移至110℃的真空烘箱中干燥，得到正极极片。
图34中，(a)表示制备浆料的过程以及浆料涂布的过程；(b)表示干燥后得到的极片；(c)表示将本实施例制备的浆料刮涂在涂碳铝箔和常规铝箔的上电化学性能对比。(c)的横坐标表示放电比容量，纵坐标表示对金属锂负极的电压。恒流充放电的电流密度为0.13mA/cm 2。实验样品为铝箔(Al)和镀炭铝箔的集流体(C-coated Al)，CC表示集流体。测试结果表面镀炭的铝箔涂布的电极表现出较小的极化。
实施例4.6 有机相涂布电解质层
称取200毫克聚合物黏结剂(SEBR)溶解在一定量的正庚烷(heptane) 中，再加入1.8克的Li 3InCl 6，通过控制heptane的含量制成浆料，然后刮涂在铜的集流体上，100度真空干燥，干燥后电解质层剥离，可以得到固态电解质材料薄层。
图35中，(a)表示制备的超薄电解质层；(b)表示Li 3InCl 6在heptane分散前后XRD结果对比；结果表明经过heptane溶剂分散的Li3InCl6前后没有发生相变，证明Li 3InCl 6在heptane中无化学反应及物理溶解。
工业实用性
本发明公开了一种锂二次电池添加剂、电池及电极。本发明提供的锂二次电池添加剂具有高离子电导率、空气稳定性，能够改善电极离子快速传输，提高电极负载量、厚度，提高电池能量密度。本发明提供的固态电解质材料具有高的锂离子传导率。本发明提供的电极、电解质薄层可以显著提高离子电导率、化学/电化学稳定性和可塑性。本发明在二次电池技术领域具有广阔的应用前景及良好的工业实用性。

Claims (41)

  1. 一种如下式所示的锂二次电池添加剂，
    Li bM aX c，
    其中，M选自B,Al,Ga,In,Y,Sc,Sb,Bi,Nb,Ta,Ti,Zr,V,Cr,Mo,W,Mn,Tc,Re,Fe,Co,Ni,Cu,Ag,Zn,Cd,La,Ce,Pr,Nd,Pm,Sm,Eu,Gd,Tb,Dy,Ho,Er,Tm,Yb,Lu中的一种或者多种；X选自F,Cl,Br,I中的一种或者多种；0.2≤b≤6；0.1≤a≤3；1≤c≤9。
  2. 根据权利要求1所述的锂二次电池添加剂，其特征在于，
    1≤b≤3；和/或，
    0.2≤a≤1；和/或，
    3≤c≤6；
    优选地，所述锂二次电池添加剂如下任一式所示，
    Li 3Y 1-dIn dCl 6，其中，0≤d≤1；进一步地，d选自0,0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9或1.0；
    Li 3InCl 6，或Li 3NbCl 8，或Li 3YCl 6。
  3. 根据权利要求1或2所述的锂二次电池添加剂，其特征在于，所述锂二次电池添加剂为玻璃相、玻璃-陶瓷相或结晶相。
  4. 权利要求1-3任一项所述的锂二次电池添加剂的制备方法，其特征在于，
    将所需原料或前驱物按配比混合后研磨而制得；或者进一步采用有机溶剂共溶重结晶法，加热共熔法，不溶性烃类有机溶剂中使原料颗粒相接触的方法制成相应相态的化合物。
  5. 根据权利要求4所述的制备方法，其特征在于，所述原料或前驱物包括LiX和MX y前驱物，其中M、X的定义与权利要求1-3任一项相同；1≤y≤6，优选地，2≤y≤5。
  6. 根据权利要求4或5所述的制备方法，其特征在于，在所需原料或前驱物的混合过程中还添加适量助溶剂、助熔剂或者络合物的配体，具体包括NH 4Cl、I 2、LiI或S。
  7. 根据权利要求4-6任一项所述的制备方法，其特征在于，通过加热退火的方法将所获得的玻璃相或玻璃-陶瓷相中间产物转变为玻璃-陶瓷相 或结晶相；
    其中，所述加热退火温度优选为100-600℃，更优选150-350℃；所述加热退火时间优选为10分钟-24小时，更优选1-10小时；
    进一步优选地，所述加热退火过程中还加入NH 4Cl、I 2、LiI、S、P或二茂铁进行物相和形貌的调控。
  8. 权利要求4-7任一项所述的方法制备的锂二次电池添加剂。
  9. 权利要求1-3、8任一项所述的锂二次电池添加剂在锂二次电池中作为电极添加剂的应用，或者在制备锂二次电池中的应用；
    其中，所述锂二次电池优选包括液相锂二次电池、半固态以及全固态锂二次电池。
  10. 一种锂二次电池，其特征在于，该电池的正极层、电解质层和负极层中至少一者含有：一种或者多种权利要求1-3、8任一项所述的锂二次电池添加剂；
    其中，所述锂二次电池优选包括液相锂二次电池、半固态以及全固态锂二次电池。
  11. 一种如下式所示的二次电池固态电解质材料，
    A 1-3zIn zX；
    其中，A选自Li、Na、K、Cs中的一种或者多种；X选自F,Cl,Br,I中的一种或者多种；0<z≤0.33。
  12. 根据权利要求11所述的固态电解质材料，其特征在于，0.1≤z≤0.25；
    优选地，所述固态电解质材料如下任一式所示，
    Li 4InCl 7；
    Li 3InCl 5F；
    Li 1-3zIn zCl，z为0.25,0.2,0.167,0.143或0.1；或，
    Na 3InCl 4Br 2。
  13. 根据权利要求11或12所述的固态电解质材料，其特征在于，其中的In被以下元素部分或者全部取代：Al、Ga、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Fe、Bi、Sb、Cr、Co、Zr、Zn、Cd、Mg中的一种或者多种；
    优选地，所述固态电解质材料如下任一式所示，Li 3In 0.8Y 0.2Cl 6，或Li 2In 0.1Zn 0.9Cl 4.1，或LiGaCl 4，或Li 6FeCl 8，或Li 3YCl 6，或Li 3BiCl 6。
  14. 根据权利要求11-13任一项所述的固态电解质材料，其特征在于，所述固态电解质材料可为玻璃相、玻璃-陶瓷相或结晶相；
    或者，所述固态电解质材料包含主结晶相，在所述结晶相为扭曲的岩盐相结构；
    或者，所述固态电解质材料可包含异种晶相，所述异种晶相与主结晶相具有不同的晶体结构排列；
    或者，所述固态电解质材料可包含非晶相。
  15. 权利要求11-14任一项所述固态电解质材料的制备方法，其特征在于，采用水相法进行制备；所用的原料或前驱物包括但不限于AX、InX 3和MX a；其中A、X的定义与权利要求11-14任一项含义相同；M为Al、Ga、Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Fe、Bi、Sb、Cr、Co、Zr、Zn、Cd、Mg中的一种或者多种；2≤a≤4；
    优选地，所用的原料或前驱物为所述AX、InX 3或MX a的水合物或者溶液；或者，优选所用的原料或前驱物为可在水相中游离或反应出具有等同离子作用的所述AX、InX 3或MX a的前驱物，所述前驱物包括但不限于碳酸盐，碳酸氢盐；
    或者，优选地，所述水相法在制备过程中适当加入HCl、NH 4Cl作为水解抑制剂或者配位剂。
  16. 根据权利要求15所述的制备方法，其特征在于，包括：将所需原料或前驱物以一定的比例溶于水相中，所需原料或前驱物与水相的质量比为1:0.5～1:15，优选1:2～1:5；
    进一步优选地，所述水相为去离子水或有机溶剂或有机溶剂/水的混合溶剂；更优选地，所述有机溶剂为乙醇。
  17. 根据权利要求15或16所述的制备方法，其特征在于，所述水相法在干燥后可进行退火处理，退火温度为100～600℃，优选120～500℃；
    优选地，所述退火在空气气氛、惰性气体气氛或者真空气氛中进行。
  18. 权利要求15-17任一项所述方法制备的固态电解质材料。
  19. 权利要求11-14、18任一项所述固态电解质材料在制备二次电池中的应用，其中所述二次电池包括锂二次电池和钠二次电池。
  20. 一种二次电池，包括正极(层)，负极(层)，以及在所述正极(层)和负极(层)之间的电解质层；所述正极(层)、负极(层)和电解质层中至少一者含有一种或者多种权利要求11-14、18任一项所述固态电解质材料；其中所述二次电池包括锂二次电池和钠二次电池。
  21. 固态电解质材料，其特征在于，
    具有Li 3b-3aIn aCl 3所示的组成，其中0.2≤a≤0.8，0.9≤b≤1.15；
    还具有第1晶相，该第1晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝14.6°±0.15°、16.7°±0.15°和34.3°±0.15°的位置具有峰。
  22. 根据权利要求21所述的固态电解质材料，其特征在于，在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(131)面的X射线强度设为I (131)，此时，满足I (001)/I (131)>0.6；优选地，I (001)/I (131)>0.8。
  23. 根据权利要求21或22所述的固态电解质材料，其特征在于，在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(110)面的X射线强度设为I (110)，此时，满足I (110)/I (001)<0.85；优选地，I (110)/I (001)<0.65。
  24. 根据权利要求21-23任一项所述的固态电解质材料，其特征在于，还包含异种晶相，所述异种晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝10.8°±0.2°的位置具有峰；
    优选地，所述异种晶相具有与所述第1晶相不同的晶体结构，且所述异种晶相介于所述第1晶相之间。
  25. 根据权利要求21-24任一项所述的固态电解质材料，其特征在于，还包含非晶相；优选地，所述非晶相介于所述第1晶相之间。
  26. 根据权利要求21-25任一项所述的固态电解质材料，其特征在于，0.3≤a≤0.7，0.95≤b≤1.10；优选地，a为0.53，b为1.03。
  27. 根据权利要求21-26任一项所述的固态电解质材料，其特征在于，具有>10 -3S/cm的离子传导率；优选具有0.7-2.5mS/cm的离子传导率，或 者具有1.0-2.0mS/cm的离子传导率。
  28. 根据权利要求21-27任一项所述的固态电解质材料，其特征在于，具有Li 1.5In 0.53Cl 3所示的组成；优选地，该材料在室温条件下离子传导率为2mS/cm。
  29. 根据权利要求21-28任一项所述的固态电解质材料，其特征在于，所述固态电解质材料的X射线衍射图如图24所示。
  30. 全固态锂电池，其特征在于，具有正极活性物质层、负极活性物质层以及形成于上述正极活性物质层和上述负极活性物质层之间的固态电解质层，其中，所述正极活性物质层、所述负极活性物质层和所述固态电解质层中的至少一者含有权利要求21-29任一项所述的固态电解质材料。
  31. 一种电极，其特征在于，包括：固态电解质材料，电极材料，导电剂和黏结剂；其中，
    所述固态电解质材料为Li aMX b，M为Al、Ga、In、Sc、Y、La系中的一种或者几种，X为F、Cl、Br中的一种或者多种，0≤a≤10，1≤b≤13；优选地，所述固态电解质材料选自Li 3InCl 6、Li 3YCl 6、Li 3YBr 6、Li 3HoCl 6、Li 3ScCl 6中的一种或几种；或者，
    所述固态电解质材料具有Li 3b-3aIn aCl 3所示的组成，其中0.2≤a≤0.8，0.9≤b≤1.15；还具有第1晶相，该第1晶相在使用了铜Kα射线的X射线衍射测定中，在2θ＝14.6°±0.15°、16.7°±0.15°和34.3°±0.15°的位置具有峰；优选地，0.3≤a≤0.7，0.95≤b≤1.10；更优选地，a为0.53，b为1.03。
  32. 根据权利要求31所述的电极，其特征在于，该Li 3b-3aIn aCl 3所示的固态电解质材料，
    在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(131)面的X射线强度设为I (131)，此时，满足I (001)/I (131)>0.6；优选地，I (001)/I (131)>0.8；和/或，
    在所述第1晶相中，将该晶体结构中的(001)面的X射线强度设为I (001)，并将该晶体结构中的(110)面的X射线强度设为I (110)，此时，满足I (110)/I (001)<0.85；优选地，I (110)/I (001)<0.65。
  33. 根据权利要求31或32所述的电极，其特征在于，该Li 3b-3aIn aCl 3所示的固态电解质材料还包含异种晶相，所述异种晶相在使用了铜Kα射 线的X射线衍射测定中，在2θ＝10.8°±0.2°的位置具有峰；
    优选地，所述异种晶相具有与所述第1晶相不同的晶体结构，且所述异种晶相介于所述第1晶相之间。
  34. 根据权利要求31-33任一项所述的电极，其特征在于，该Li 3b-3aIn aCl 3所示的固态电解质材料还包含非晶相；优选地，所述非晶相介于所述第1晶相之间。
  35. 根据权利要求31-34任一项所述的电极，其特征在于，该Li 3b-3aIn aCl 3所示的固态电解质材料的X射线衍射图如图24所示。
  36. 根据权利要求31-35任一项所述的电极，其特征在于，所述电极材料包覆于所述固态电解质材料中；其中，所述电极材料与固态电解质材料的重量比优选为(95:5)-(70:30)，更优选为85:15。
  37. 根据权利要求31-36任一项所述的电极，其特征在于，所述电极中电极材料的含量为50wt％到98wt％，和/或，所述固态电解质材料的含量为2wt％到50wt％，和/或，所述导电剂的含量为1wt％到10％，和/或，黏结剂的含量为1wt％到10％。
  38. 权利要求31-37任一项所述电极的制备方法，其特征在于，包括将所述固态电解质材料或其前躯体溶于水中，再加入电极材料，混匀，干燥，然后再进一步真空脱水干燥即可；或者制备方法包括将所述固态电解质材料或其前躯体，以及电极材料溶于有机溶剂中，超声分散，干燥，然后再进一步真空脱溶剂干燥，即可。
  39. 一种电解质薄层，其特征在于，包括固态电解质材料和黏结剂；其中所述固态电解质材料与权利要求31-37任一项所述的固态电解质材料相同；
    优选地，所述固态电解质材料的含量为20wt％到100wt％，更优选45wt％到99wt％；黏结剂的含量为0到80wt％，更优选1wt％到55wt％。
  40. 权利要求39所述电解质薄层的制备方法，其特征在于，包括将黏结剂溶于溶剂中，再加入固态电解质材料或其前躯体和导电剂制成浆料，然后涂布在集流体或柔性基底上，干燥，再从所述集流体或柔性基底上剥离，即可。
  41. 一种二次电池，其特征在于，包括权利要求31-37任一项所述的 电极或权利要求39所述电解质薄层；所述二次电池优选为锂/锂离子二次电池。
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