WO2022246747A1 - Metal-hydrogen battery and preparation method therefor - Google Patents

Metal-hydrogen battery and preparation method therefor Download PDF

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WO2022246747A1
WO2022246747A1 PCT/CN2021/096432 CN2021096432W WO2022246747A1 WO 2022246747 A1 WO2022246747 A1 WO 2022246747A1 CN 2021096432 W CN2021096432 W CN 2021096432W WO 2022246747 A1 WO2022246747 A1 WO 2022246747A1
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metal
solid electrolyte
hydrogen
electrode
electrolyte
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PCT/CN2021/096432
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French (fr)
Chinese (zh)
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陈维
刘再春
朱正新
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中国科学技术大学
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M12/00—Hybrid cells; Manufacture thereof
    • H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
    • H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • the disclosure belongs to the technical field of electrochemistry, and in particular relates to a metal-hydrogen battery and a preparation method thereof.
  • the present disclosure provides a metal-hydrogen battery and a preparation method thereof, in order to at least partly solve the above technical problems.
  • the present disclosure provides a metal-hydrogen battery, including: a positive electrode, a negative electrode, and an electrolyte; wherein the positive electrode includes a hydrogen electrode, wherein the hydrogen electrode includes a positive electrode sheet containing a positive active material.
  • the negative electrode includes a metal electrode, wherein the metal electrode includes a main metal and a doping metal, wherein the main metal includes one or more of Li, Na, K, Ca, Mg, Al; the doping metal includes Ni, Zn, Sr , one or more of Ba.
  • the electrolyte includes an inorganic electrolyte on the positive side, an organic electrolyte on the negative side, and a solid electrolyte that separates the inorganic electrolyte and the organic electrolyte.
  • the molar content of the doping metal is 0.01-10% of that of the main metal.
  • the positive electrode active material includes one or more of a first metal catalyst, a second metal catalyst, a third metal catalyst, and a carbon material.
  • the first metal catalyst includes Pt, Pd, Ir, Ru, PtNi, PtCo, PtMo, PtW, PtNiCo, PtNiMo, PdNi, PdCo, PdMo, PdW, PdNiCo, PdNiMo, IrNi, IrCo, IrMo, IrW , IrNiCo, IrNiMo, RuNi, RuCo, RuMo, RuW, RuNiCo, RuNiMo in one or more.
  • the second metal catalyst includes one or more of PtO 2 , PtOH, PtC, IrO 2 , IrC, IrN, IrS, IrP, RuO 2 , RuC, RuN, RuS, and RuP;
  • the third metal catalyst includes Ni, NiMo, NiCoMo, MoC, MoC 2 , MoO 2 , MoS 2 , MoP, WC, WC 2 , WO 2 , WS 2 , WP, NiN, NiS, NiP, NiPS one or more of
  • the carbon material includes one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, and nanotubes.
  • the inorganic electrolyte solution includes a first metal salt and water, wherein the first metal salt includes one or more of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt.
  • the organic electrolytic solution includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of lithium salt, potassium salt, and sodium salt.
  • the organic solvent includes one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, and dimethyl sulfoxide.
  • the solid electrolyte includes one or both of the first solid electrolyte and the second solid electrolyte.
  • the first solid electrolyte includes an amorphous sulfide solid electrolyte, a perovskite solid electrolyte, a sodium superconducting solid electrolyte, a lithium superconducting solid electrolyte, a garnet solid electrolyte, a layered lithium One or more of type solid electrolyte, glass-ceramic solid electrolyte.
  • the second solid electrolyte includes one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride.
  • the present disclosure also provides a method for preparing the above-mentioned metal-hydrogen battery, comprising: coating the positive electrode active material on the electrode material to prepare the positive electrode sheet under normal temperature and pressure air environment, and applying the positive electrode The sheet is in contact with the inorganic electrolyte to complete the preparation of the hydrogen electrode.
  • the metal electrode In an anhydrous and oxygen-free environment, the metal electrode is contacted with an organic electrolyte to complete the preparation of the metal electrode.
  • a solid electrolyte is added between the inorganic electrolyte and the organic electrolyte as a diaphragm. Assemble the hydrogen electrode, the metal electrode and the separator in the battery device, and fill the battery device with hydrogen to complete the preparation of the metal-hydrogen battery.
  • the metal-hydrogen battery involved in the present disclosure uses a hydrogen electrode as the positive electrode and a metal electrode of a low-potential metal as the negative electrode. Since the electrode potentials of the metal electrode and the hydrogen electrode are both higher than 1.6V, the metal-hydrogen battery can obtain higher than 1.6V.
  • the operating voltage of 1.6V breaks through the voltage window limit of the existing hydrogen battery system operating voltage lower than 1.4V.
  • Fig. 1 schematically shows the structural representation of metal-hydrogen battery
  • Fig. 2 schematically shows the charging curves of the first 2 lithium metal-hydrogen batteries prepared in Example 1;
  • Fig. 3 schematically shows the first charge-discharge curve of the sodium metal-hydrogen battery prepared in Example 2 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
  • Fig. 4 schematically shows the first charge-discharge curve of the potassium metal-hydrogen battery prepared in Example 3 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
  • Fig. 5 schematically shows the first charge-discharge curve of the calcium metal-hydrogen battery prepared in Example 4 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
  • Fig. 6 schematically shows the first charge-discharge curve of the magnesium metal-hydrogen battery prepared in Example 5 subjected to a cycle test with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the present disclosure provides a metal-hydrogen battery, comprising: a positive electrode, a negative electrode, and an electrolyte; wherein the positive electrode includes a hydrogen electrode, wherein the hydrogen electrode includes a positive electrode sheet containing a positive active material.
  • the negative electrode includes a metal electrode, wherein the metal electrode includes a main metal and a doping metal, wherein the main metal includes one or more of Li, Na, K, Ca, Mg, Al; the doping metal includes Ni, Zn, Sr , one or more of Ba.
  • the electrolyte includes an inorganic electrolyte on the positive side, an organic electrolyte on the negative side, and a solid electrolyte that separates the inorganic electrolyte and the organic electrolyte.
  • the hydrogen electrode is used as the positive electrode
  • the metal electrode of a low-potential metal is used as the negative electrode
  • the combination of the inorganic electrolyte and the organic electrolyte is used as the electrolyte. Since the electrode potentials of the metal electrode and the hydrogen electrode are both higher than 1.6V , so that the metal-hydrogen battery can obtain a working voltage higher than 1.6V, breaking through the voltage window limit of the working voltage of the existing hydrogen battery system lower than 1.4V.
  • the metal electrodes include but not limited to main metals and doped metals, and also include mixtures of main metals and nano-carbon materials.
  • the nano-carbon material can be one or more of nanospheres, nanoparticles, nanosheets, nanowires, and nanotubes.
  • the molar content of the doping metal is 0.01-10% of that of the main metal.
  • 0.01%, 1%, 3%, 5%, 8%, 10% is 0.01-10% of that of the main metal.
  • the positive electrode active material includes one or more of a first metal catalyst, a second metal catalyst, a third metal catalyst, and a carbon material.
  • the first metal catalyst includes Pt, Pd, Ir, Ru, PtNi, PtCo, PtMo, PtW, PtNiCo, PtNiMo, PdNi, PdCo, PdMo, PdW, PdNiCo, PdNiMo, IrNi, IrCo, IrMo, IrW , IrNiCo, IrNiMo, RuNi, RuCo, RuMo, RuW, RuNiCo, RuNiMo in one or more.
  • the second metal catalyst includes one or more of PtO 2 , PtOH, PtC, IrO 2 , IrC, IrN, IrS, IrP, RuO 2 , RuC, RuN, RuS, and RuP;
  • the third metal catalyst includes Ni, NiMo, NiCoMo, MoC, MoC 2 , MoO 2 , MoS 2 , MoP, WC, WC 2 , WO 2 , WS 2 , WP, NiN, NiS, NiP, NiPS one or more of
  • the carbon material includes one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, and nanotubes.
  • the inorganic electrolyte solution includes a first metal salt and water, wherein the first metal salt includes one or more of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt.
  • the organic electrolytic solution includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of lithium salt, potassium salt, and sodium salt.
  • lithium salts include but are not limited to LiPF 6 , LiClO 4 , LiTFSI, Li 2 SO 4 , LiBF 4 , LiBOB, Li 2 CO 3 , LiHCO 3 , LiAc, LiNO 3 , LiBH 4 .
  • sodium salts include but are not limited to NaClO 4 , NaBF 4 , NaPF 6 , NaBOB, Na 2 CO 3 , NaHCO 3 , NaNO 3 , and NaBH 4 .
  • potassium salts include but are not limited to KClO 4 , KBF 4 , KPF 6 , KBOB, K 2 CO 3 , KNO 3 , KHCO 3 , K 2 SO 4 , and KBH 4 .
  • magnesium salts include but are not limited to MgCl 2 , MgF 2 , MgCO 3 , MgSO 4 , Mg(Ac) 2 , Mg(ClO 4 ) 2 , and Mg(NO 3 ) 2 .
  • calcium salts include but are not limited to CaCl 2 , CaF 2 , CaCO 3 , CaSO 4 , Ca(OCl) 2 , CaHPO 4 , Ca(H 2 PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Ca(NO 3 ) 2 .
  • aluminum salts include but are not limited to AlCl 3 , AlF 3 , AlH(CO 3 ) 2 , Al 2 (SO 4 ) 3 , AlPO 4 , Al(NO 3 ) 3 .
  • the inorganic electrolyte includes but is not limited to pure aqueous solution, and also includes gel aqueous solution and high-concentration aqueous solution with metal ion concentration greater than 60%.
  • the inorganic electrolyte includes but not limited to acidic solution, neutral solution, and alkaline solution.
  • the inorganic electrolyte is an alkaline solution
  • the inorganic electrolyte also includes metal hydroxides, such as LiOH, NaOH, KOH, Mg(OH) 2 , Al(OH) 3 .
  • the organic solvent includes one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, and dimethyl sulfoxide.
  • the solid electrolyte includes one or both of the first solid electrolyte and the second solid electrolyte.
  • the first solid electrolyte includes an amorphous sulfide solid electrolyte, a perovskite solid electrolyte, a sodium superconducting solid electrolyte, a lithium superconducting solid electrolyte, a garnet solid electrolyte, a layered lithium One or more of type solid electrolyte, glass-ceramic solid electrolyte.
  • the amorphous sulfide type solid electrolyte includes but not limited to Li 10 GeP 2 S 12
  • the perovskite (Perovskite) type solid electrolyte includes but not limited to Li 0.38 Sr 0.44 Ta 0.7 Hf 0.3 O 2.95 F 0.05
  • sodium superconducting (NASICON) type solid electrolyte including but not limited to LiZr 2 (PO 4 ) 3
  • garnet (Garnet) type solid electrolyte including but not limited to Li 7 La 3 Zr 2 O 12
  • layered lithium type solid electrolyte including But not limited to Li 3 N
  • glass-ceramic solid electrolytes include but not limited to Li 2.99 Ca 0.005 OCl.
  • the second solid electrolyte includes one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride.
  • the present disclosure also provides a method for preparing the above-mentioned metal-hydrogen battery, which includes: coating the positive electrode active material on the electrode material to prepare the positive electrode sheet under normal temperature and normal pressure air environment, and contacting the positive electrode sheet with the inorganic electrolyte to complete Preparation of the hydrogen electrode.
  • the metal electrode In an anhydrous and oxygen-free environment, the metal electrode is contacted with an organic electrolyte to complete the preparation of the metal electrode.
  • a solid electrolyte is added between the inorganic electrolyte and the organic electrolyte as a diaphragm. Assemble the hydrogen electrode, the metal electrode and the separator in the battery device, and fill the battery device with hydrogen to complete the preparation of the metal-hydrogen battery.
  • lithium-ion-hydrogen batteries sodium metal-hydrogen batteries, potassium metal-hydrogen batteries, calcium metal-hydrogen batteries, magnesium metal-hydrogen batteries, aluminum metal-hydrogen batteries, lithium-aluminum metal-hydrogen batteries, and doped lithium-aluminum batteries.
  • the alloy metal-hydrogen battery is taken as an example to describe the present disclosure in detail.
  • the battery assembly structures in the following Examples 1-8 are all shown in Figure 1, including hydrogen gas 1, positive electrode active material 2, inorganic electrolyte 3, solid electrolyte 4, organic electrolyte 5, and metal negative electrode 6 from top to bottom.
  • Li 2 SO 4 Under normal temperature and pressure air environment, weigh a certain mass of Li 2 SO 4 and fully dissolve it in deionized water to mix and prepare a 2mol/L Li 2 SO 4 aqueous solution, using NASICON-type LiZr 2 (PO 4 ) 3 as a solid electrolyte material .
  • NASICON-type LiZr 2 (PO 4 ) 3 is used as solid electrolyte material
  • high voltage (3.04V) lithium metal is used as negative electrode material
  • 5% mass fraction of platinum carbon catalyst is used as active material of positive electrode
  • polyvinylidene fluoride is used Using N-methyl-pyrrolidone as a binder and N-methyl-pyrrolidone as a solvent, stir it into a uniform slurry, and then coat it on the gas conductive layer to make a positive electrode sheet.
  • the battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the test instrument is a LAND battery test system.
  • the test results are shown in Figure 2.
  • the upper curve in Figure 2 is the charging curve, and the lower curve is the discharging curve.
  • the highest discharge voltage of the discharging curve is close to 2.85V.
  • NASICON-type NaZr 2 (PO 4 ) 3 is used as solid electrolyte material
  • high-voltage (2.71V) sodium metal is used as negative electrode material
  • 5% mass fraction of platinum carbon catalyst is used as positive electrode active material
  • polyvinylidene fluoride Ethylene is used as a binder and N-methyl-pyrrolidone is used as a solvent. After being stirred into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet.
  • the battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the test instrument is a LAND battery test system.
  • the test results are shown in Figure 3.
  • the upper curve in Figure 3 is the charging curve, and the lower curve is the discharging curve.
  • the highest discharge voltage of the discharging curve is close to 2.5V.
  • K 2 SO 4 Under normal temperature and pressure air environment, take a certain mass of K 2 SO 4 and fully dissolve it in deionized water to mix and prepare a 2mol/L K 2 SO 4 aqueous solution, use K 2 PInS 4 as a solid electrolyte material, and use a high voltage (2.92V ) of potassium metal as the negative electrode material, 5% mass fraction of platinum carbon catalyst as the active material of the positive electrode, with polyvinylidene fluoride as the binder, N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, coating Distributed on the gas conductive layer to make a positive pole piece.
  • anhydrous and oxygen-free glove box use the above-mentioned potassium metal ion migration K 2 PInS 4 solid electrolyte, drop an electrolyte solution (1mol/L KClO 4 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g In order to eliminate the interfacial resistance, it is assembled with potassium metal to obtain a potassium metal anode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned K 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side.
  • the battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the test instrument is a LAND battery test system.
  • the test results are shown in Figure 4.
  • the upper curve in Figure 4 is the charging curve, and the lower curve is the discharge curve.
  • the highest discharge voltage of the discharge curve is close to 2.7V.
  • the battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the test instrument is a LAND battery test system. The test results are shown in Figure 5.
  • the upper curve in Figure 5 is the charging curve, and the lower curve is the discharge curve.
  • the highest discharge voltage of the discharge curve is close to 2.5V.
  • anhydrous and oxygen-free glove box use the above-mentioned magnesium metal ion migration PEO polymer solid electrolyte, drop an electrolyte solution (1mol/L MgCl 2 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g to eliminate Interfacial resistance, assembled with magnesium metal to obtain magnesium metal negative electrode.
  • an electrolyte solution (1mol/L MgCl 2 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g to eliminate Interfacial resistance, assembled with magnesium metal to obtain magnesium metal negative electrode.
  • an electrolyte solution (1mol/L MgCl 2 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g to eliminate Interfacial resistance
  • an electrolyte solution (1mol/L MgCl 2 , solvent EC/DMC/EMC
  • solvent EC/DMC/EMC solvent EC/DMC/EMC
  • the battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g.
  • the test instrument is a LAND battery test system.
  • the test results are shown in Figure 6.
  • the upper curve in Figure 6 is the charging curve, and the lower curve is the discharging curve.
  • the highest discharge voltage of the discharging curve is close to 2.3V.
  • NASICON-type LiZr 2 (PO4) 3 is used as solid electrolyte material
  • high voltage (3.04V) lithium aluminum alloy metal is used as negative electrode material
  • 5% mass fraction of platinum carbon catalyst is used as active material of positive electrode
  • polyvinylidene fluoride Ethylene is used as a binder and N-methyl-pyrrolidone is used as a solvent. After being stirred into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet.
  • Li 2 SO 4 Under normal temperature and pressure air environment, weigh a certain mass of Li 2 SO 4 and fully dissolve it in deionized water to prepare a 2mol/L Li2SO4 aqueous solution, using NASICON-type LiZr 2 (PO4) 3 as a solid electrolyte material.
  • NASICON-type LiZr 2 (PO4) 3 is used as a solid electrolyte material, and a high-voltage (3.04V) Ba-doped lithium aluminum alloy metal is used as a negative electrode material, wherein the Ba content is 1% of the lithium mass fraction, 5% mass fraction
  • the platinum carbon catalyst is the active material of the positive electrode, with polyvinylidene fluoride as the binder and N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet .

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Abstract

The present disclosure provides a metal-hydrogen battery and a preparation method therefor, wherein the metal-hydrogen battery comprises a positive electrode, a negative electrode and an electrolyte solution, and the positive electrode comprises a hydrogen electrode, which comprises a positive electrode plate containing a positive electrode active material. The negative electrode comprises a metal electrode, which comprises a main metal and a doped metal, wherein the main metal comprises one or more of Li, Na, K, Ca, Mg and Al, and the doped metal comprises one or more of Ni, Zn, Sr and Ba. The electrolyte solution comprises an inorganic electrolyte solution on the positive electrode side, an organic electrolyte solution on the negative electrode side and a solid electrolyte for separating the inorganic electrolyte solution from the organic electrolyte solution.

Description

金属-氢气电池及其制备方法Metal-hydrogen battery and its preparation method 技术领域technical field
本公开属于电化学技术领域，具体涉及一种金属-氢气电池及其制备方法。The disclosure belongs to the technical field of electrochemistry, and in particular relates to a metal-hydrogen battery and a preparation method thereof.
背景技术Background technique
随着全球信息时代的高速发展，对储能设备的需求在快速增长。在相关技术中，利用氢气电极优异的特点，与镍正极进行匹配，得到了具有较高能量密度和长时间稳定的镍-氢气电池。这种镍-氢气电池储能技术被应用到航天飞行器和卫星上，使用寿命超过十五年。氢气作为目前已知相对分子质量最轻的物质，具有高理论容量，且绿色环保、资源丰富，广泛存在于宇宙中，氢能已被视为全球具有发展潜力的清洁能源之一。另外，采用优异的双功能催化剂去催化氢气的氧化与还原反应，表现出高容量、低的过电位与稳定的使用寿命。因此，将氢气作为电池的电极，能获得高的能量和功率密度以及长的工作寿命。然而这种传统镍-氢气电池受限于水系电解液有限的电压窗口，放电平台仅为1.2V，且催化剂价格昂贵，阻碍了其广泛的应用。With the rapid development of the global information age, the demand for energy storage equipment is growing rapidly. In related technologies, a nickel-hydrogen battery with high energy density and long-term stability has been obtained by utilizing the excellent characteristics of the hydrogen electrode and matching it with the nickel positive electrode. This nickel-hydrogen battery energy storage technology is applied to space vehicles and satellites, with a service life of more than fifteen years. Hydrogen, as the lightest substance known at present, has a high theoretical capacity, is green and environmentally friendly, and is rich in resources. It exists widely in the universe. Hydrogen energy has been regarded as one of the clean energy sources with development potential in the world. In addition, an excellent bifunctional catalyst is used to catalyze the oxidation and reduction reactions of hydrogen, showing high capacity, low overpotential and stable service life. Therefore, using hydrogen as the electrode of the battery can obtain high energy and power density and long working life. However, this traditional nickel-hydrogen battery is limited by the limited voltage window of the aqueous electrolyte, the discharge platform is only 1.2V, and the catalyst is expensive, which hinders its wide application.
发明内容Contents of the invention
有鉴于此，本公开提供了一种金属-氢气电池及其制备方法，以期至少部分地解决上述技术问题。In view of this, the present disclosure provides a metal-hydrogen battery and a preparation method thereof, in order to at least partly solve the above technical problems.
作为本公开的一个方面，本公开提供了一种金属-氢气电池，包括：正极、负极、电解液；其中，正极包括氢气电极，其中，氢气电极包括含有正极活性物质的正极极片。负极包括金属电极，其中，金属电极包括主金属和掺杂金属，其中，主金属包括Li、Na、K、Ca、Mg、Al中的一种或多种；掺杂金属包括Ni、Zn、Sr、Ba中的一种或多种。电解液包括正极侧的无机电解液、负极侧的有机电解液和分离无机电解液和有机电解液的固态电解质。As an aspect of the present disclosure, the present disclosure provides a metal-hydrogen battery, including: a positive electrode, a negative electrode, and an electrolyte; wherein the positive electrode includes a hydrogen electrode, wherein the hydrogen electrode includes a positive electrode sheet containing a positive active material. The negative electrode includes a metal electrode, wherein the metal electrode includes a main metal and a doping metal, wherein the main metal includes one or more of Li, Na, K, Ca, Mg, Al; the doping metal includes Ni, Zn, Sr , one or more of Ba. The electrolyte includes an inorganic electrolyte on the positive side, an organic electrolyte on the negative side, and a solid electrolyte that separates the inorganic electrolyte and the organic electrolyte.
根据本公开实施例，掺杂金属的摩尔含量为主金属摩尔含量的0.01～10％。According to an embodiment of the present disclosure, the molar content of the doping metal is 0.01-10% of that of the main metal.
根据本公开实施例，正极活性物质包括第一金属催化剂、第二金属催化剂、第三金属催化剂、碳材料中的一种或多种。According to an embodiment of the present disclosure, the positive electrode active material includes one or more of a first metal catalyst, a second metal catalyst, a third metal catalyst, and a carbon material.
根据本公开实施例，第一金属催化剂包括Pt、Pd、Ir、Ru、PtNi、PtCo、PtMo、PtW、PtNiCo、PtNiMo、PdNi、PdCo、PdMo、PdW、PdNiCo、PdNiMo、IrNi、IrCo、IrMo、IrW、IrNiCo、IrNiMo、RuNi、RuCo、RuMo、RuW、RuNiCo、RuNiMo中的一种或多种。According to an embodiment of the present disclosure, the first metal catalyst includes Pt, Pd, Ir, Ru, PtNi, PtCo, PtMo, PtW, PtNiCo, PtNiMo, PdNi, PdCo, PdMo, PdW, PdNiCo, PdNiMo, IrNi, IrCo, IrMo, IrW , IrNiCo, IrNiMo, RuNi, RuCo, RuMo, RuW, RuNiCo, RuNiMo in one or more.
根据本公开实施例，第二金属催化剂包括PtO 2、PtOH、PtC、IrO 2、IrC、IrN、IrS、IrP、RuO 2、RuC、RuN、RuS、RuP中的一种或多种； According to an embodiment of the present disclosure, the second metal catalyst includes one or more of PtO 2 , PtOH, PtC, IrO 2 , IrC, IrN, IrS, IrP, RuO 2 , RuC, RuN, RuS, and RuP;
根据本公开实施例，第三金属催化剂包括Ni、NiMo、NiCoMo、MoC、MoC 2、MoO 2、MoS 2、MoP、WC、WC 2、WO 2、WS 2、WP、NiN、NiS、NiP、NiPS中的一种或多种； According to an embodiment of the present disclosure, the third metal catalyst includes Ni, NiMo, NiCoMo, MoC, MoC 2 , MoO 2 , MoS 2 , MoP, WC, WC 2 , WO 2 , WS 2 , WP, NiN, NiS, NiP, NiPS one or more of
根据本公开实施例，碳材料包括微米球、纳米球、微米颗粒、纳米颗粒、微米片、纳米片、微米线、纳米线、微米管、纳米管中的一种或多种。According to an embodiment of the present disclosure, the carbon material includes one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, and nanotubes.
根据本公开实施例，无机电解液包括第一金属盐和水，其中，第一金属盐包括锂盐、钠盐、钾盐、镁盐、钙盐、铝盐中的一种或多种。According to an embodiment of the present disclosure, the inorganic electrolyte solution includes a first metal salt and water, wherein the first metal salt includes one or more of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt.
根据本公开实施例，有机电解液包括第二金属盐和有机溶剂，其中，第二金属盐包括锂盐、钾盐、钠盐中的一种或多种。According to an embodiment of the present disclosure, the organic electrolytic solution includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of lithium salt, potassium salt, and sodium salt.
根据本公开实施例，有机溶剂包括乙腈、四氢呋喃、乙烯碳酸酯、丙烯碳酸酯、二乙基碳酸酯、二甲基碳酸酯、二甲基亚砜中的一种或多种。According to an embodiment of the present disclosure, the organic solvent includes one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, and dimethyl sulfoxide.
根据本公开实施例，固态电解质包括第一固态电解质、第二固态电解质中的一种或两种。According to an embodiment of the present disclosure, the solid electrolyte includes one or both of the first solid electrolyte and the second solid electrolyte.
根据本公开实施例，第一固态电解质包括非晶态硫化物型固态电解质、钙钛矿型固态电解质、钠超导型固态电解质、锂超导型固态电解质、石榴石型固态电解质、层状锂型固态电解质、玻璃-陶瓷固态电解质中的一种或多种。According to an embodiment of the present disclosure, the first solid electrolyte includes an amorphous sulfide solid electrolyte, a perovskite solid electrolyte, a sodium superconducting solid electrolyte, a lithium superconducting solid electrolyte, a garnet solid electrolyte, a layered lithium One or more of type solid electrolyte, glass-ceramic solid electrolyte.
根据本公开实施例，第二固态电解质包括聚氧化乙烯、聚丙烯晴、聚甲基丙烯酸甲酯、聚偏氟乙烯中的一种或多种。According to an embodiment of the present disclosure, the second solid electrolyte includes one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride.
作为本公开的另一方面，本公开还提供了制备上述金属-氢气电池的方法，包括：在常温常压空气环境下，将正极活性物质涂布在电极材料上制备正极极片，将正极极片与无机电解液接触，完成氢气电极的制备。在无水无氧环境下，将金属电极与有机电解液接触，完成金属电极的制备。在无机电解液与有机电解液之间加入固态电解质作为隔膜。将氢气电极、金属电极、隔膜组装在电池装置中，并向电池装置中充入氢气，完成金属-氢气电池的制备。As another aspect of the present disclosure, the present disclosure also provides a method for preparing the above-mentioned metal-hydrogen battery, comprising: coating the positive electrode active material on the electrode material to prepare the positive electrode sheet under normal temperature and pressure air environment, and applying the positive electrode The sheet is in contact with the inorganic electrolyte to complete the preparation of the hydrogen electrode. In an anhydrous and oxygen-free environment, the metal electrode is contacted with an organic electrolyte to complete the preparation of the metal electrode. A solid electrolyte is added between the inorganic electrolyte and the organic electrolyte as a diaphragm. Assemble the hydrogen electrode, the metal electrode and the separator in the battery device, and fill the battery device with hydrogen to complete the preparation of the metal-hydrogen battery.
本公开涉及的金属-氢气电池，以氢气电极为正极，以低电位金属的金属电极为负极，由于金属电极与氢气电极的电极电势均高于1.6V，使得该金属-氢气电池能够获得高于1.6V的工作电压，突破了现有氢气电池体系工作电压低于1.4V的电压窗口限制。The metal-hydrogen battery involved in the present disclosure uses a hydrogen electrode as the positive electrode and a metal electrode of a low-potential metal as the negative electrode. Since the electrode potentials of the metal electrode and the hydrogen electrode are both higher than 1.6V, the metal-hydrogen battery can obtain higher than 1.6V. The operating voltage of 1.6V breaks through the voltage window limit of the existing hydrogen battery system operating voltage lower than 1.4V.
附图说明Description of drawings
图1示意性地示出了金属-氢气电池的结构示意图；Fig. 1 schematically shows the structural representation of metal-hydrogen battery;
图2示意性地示出了实施例1制备的锂金属-氢气电池前2次的充电曲线；Fig. 2 schematically shows the charging curves of the first 2 lithium metal-hydrogen batteries prepared in Example 1;
图3示意性地示出了实施例2的制备的钠金属-氢气电池以500mA/g的充放电电流、2500mAh/g为指定容量进行循环测试的首次的充放电曲线；Fig. 3 schematically shows the first charge-discharge curve of the sodium metal-hydrogen battery prepared in Example 2 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
图4示意性地示出了实施例3的制备的钾金属-氢气电池以500mA/g的充放电电流、2500mAh/g为指定容量进行循环测试的首次的充放电曲线；Fig. 4 schematically shows the first charge-discharge curve of the potassium metal-hydrogen battery prepared in Example 3 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
图5示意性地示出了实施例4的制备的钙金属-氢气电池以500mA/g的充放电电流、2500mAh/g为指定容量进行循环测试的首次的充放电曲线；Fig. 5 schematically shows the first charge-discharge curve of the calcium metal-hydrogen battery prepared in Example 4 with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g as a specified capacity;
图6示意性地示出了实施例5的制备的镁金属-氢气电池以500mA/g的充放电电流、2500mAh/g为指定容量进行循环测试的首次的充放电曲线。Fig. 6 schematically shows the first charge-discharge curve of the magnesium metal-hydrogen battery prepared in Example 5 subjected to a cycle test with a charge-discharge current of 500mA/g and a specified capacity of 2500mAh/g.
具体实施方式Detailed ways
为使本公开的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本公开作进一步的详细说明。In order to make the purpose, technical solutions and advantages of the present disclosure clearer, the present disclosure will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.
近年来，新型锰-氢气电池体系、水系铁-氢气电池、酸性铅-氢气电池、中性锰-氢气电池、碱性镍-氢气电池体系等，虽然选取更高电位的电极材料可以在一定程度上提高电池的放电平台，然而并没有真正改变水系电解液电压窗口局限性的问题，使得目前的氢气电池放电电压很难突破1.6V(普遍低于1.4V)，这限制了氢气电池的规模化运用。因此，通过开发新型电池体系来扩大氢气电池的电压窗口对于构建高能量密度的储能***非常关键。In recent years, new manganese-hydrogen battery systems, aqueous iron-hydrogen batteries, acid lead-hydrogen batteries, neutral manganese-hydrogen batteries, alkaline nickel-hydrogen battery systems, etc., although the selection of higher potential electrode materials can be achieved to a certain extent However, it does not really change the limitation of the voltage window of the aqueous electrolyte, making it difficult for the current hydrogen battery discharge voltage to break through 1.6V (generally lower than 1.4V), which limits the scale of hydrogen batteries use. Therefore, expanding the voltage window of hydrogen batteries by developing new battery systems is critical for building high-energy-density energy storage systems.
本公开提供了一种金属-氢气电池，包括：正极、负极、电解液；其中，正极包括氢气电极，其中，氢气电极包括含有正极活性物质的正极极片。负极包括金属电极，其中，金属电极包括主金属和掺杂金属，其中，主金属包括Li、Na、K、Ca、Mg、Al中的一种或多种；掺杂金属包括Ni、Zn、Sr、Ba中的一种或多种。电解液包括正极侧的无机电解液、负极侧的有机电解液和分离无机电解液和有机电解液的固态电解质。The present disclosure provides a metal-hydrogen battery, comprising: a positive electrode, a negative electrode, and an electrolyte; wherein the positive electrode includes a hydrogen electrode, wherein the hydrogen electrode includes a positive electrode sheet containing a positive active material. The negative electrode includes a metal electrode, wherein the metal electrode includes a main metal and a doping metal, wherein the main metal includes one or more of Li, Na, K, Ca, Mg, Al; the doping metal includes Ni, Zn, Sr , one or more of Ba. The electrolyte includes an inorganic electrolyte on the positive side, an organic electrolyte on the negative side, and a solid electrolyte that separates the inorganic electrolyte and the organic electrolyte.
本公开实施例中，以氢气电极为正极，以低电位金属的金属电极为负极，以无机电解液与有机电解液的组合为电解液，由于金属电极与氢气电极的电极电势均高于1.6V，使得该金属-氢气电池能够获得高于1.6V的工作电压，突破了现有氢气电池体系工作电压低于1.4V的电压窗口限制。In the embodiment of the present disclosure, the hydrogen electrode is used as the positive electrode, the metal electrode of a low-potential metal is used as the negative electrode, and the combination of the inorganic electrolyte and the organic electrolyte is used as the electrolyte. Since the electrode potentials of the metal electrode and the hydrogen electrode are both higher than 1.6V , so that the metal-hydrogen battery can obtain a working voltage higher than 1.6V, breaking through the voltage window limit of the working voltage of the existing hydrogen battery system lower than 1.4V.
本公开实施例中，金属电极包括但不限于主金属和掺杂金属，还包括主金属与纳米碳材料的混合物。其中，纳米碳材料可以采用纳米球、、纳米颗粒、纳米片、纳米线、纳米管中的一种或多种。In the embodiments of the present disclosure, the metal electrodes include but not limited to main metals and doped metals, and also include mixtures of main metals and nano-carbon materials. Wherein, the nano-carbon material can be one or more of nanospheres, nanoparticles, nanosheets, nanowires, and nanotubes.
根据本公开实施例，掺杂金属的摩尔含量为主金属摩尔含量的0.01～10％。例如：0.01％、1％、3％、5％、8％、10％。According to an embodiment of the present disclosure, the molar content of the doping metal is 0.01-10% of that of the main metal. For example: 0.01%, 1%, 3%, 5%, 8%, 10%.
根据本公开实施例，正极活性物质包括第一金属催化剂、第二金属催化剂、第三金属催化剂、碳材料中的一种或多种。According to an embodiment of the present disclosure, the positive electrode active material includes one or more of a first metal catalyst, a second metal catalyst, a third metal catalyst, and a carbon material.
根据本公开实施例，第一金属催化剂包括Pt、Pd、Ir、Ru、PtNi、PtCo、PtMo、PtW、PtNiCo、PtNiMo、PdNi、PdCo、PdMo、PdW、PdNiCo、PdNiMo、IrNi、IrCo、IrMo、IrW、IrNiCo、IrNiMo、RuNi、RuCo、RuMo、RuW、RuNiCo、RuNiMo中的一种或多种。According to an embodiment of the present disclosure, the first metal catalyst includes Pt, Pd, Ir, Ru, PtNi, PtCo, PtMo, PtW, PtNiCo, PtNiMo, PdNi, PdCo, PdMo, PdW, PdNiCo, PdNiMo, IrNi, IrCo, IrMo, IrW , IrNiCo, IrNiMo, RuNi, RuCo, RuMo, RuW, RuNiCo, RuNiMo in one or more.
根据本公开实施例，第二金属催化剂包括PtO 2、PtOH、PtC、IrO 2、IrC、IrN、IrS、IrP、RuO 2、RuC、RuN、RuS、RuP中的一种或多种； According to an embodiment of the present disclosure, the second metal catalyst includes one or more of PtO 2 , PtOH, PtC, IrO 2 , IrC, IrN, IrS, IrP, RuO 2 , RuC, RuN, RuS, and RuP;
根据本公开实施例，第三金属催化剂包括Ni、NiMo、NiCoMo、MoC、MoC 2、MoO 2、MoS 2、MoP、WC、WC 2、WO 2、WS 2、WP、NiN、NiS、NiP、NiPS中的一种或多种； According to an embodiment of the present disclosure, the third metal catalyst includes Ni, NiMo, NiCoMo, MoC, MoC 2 , MoO 2 , MoS 2 , MoP, WC, WC 2 , WO 2 , WS 2 , WP, NiN, NiS, NiP, NiPS one or more of
根据本公开实施例，碳材料包括微米球、纳米球、微米颗粒、纳米颗粒、微米片、纳米片、微米线、纳米线、微米管、纳米管中的一种或多种。According to an embodiment of the present disclosure, the carbon material includes one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, and nanotubes.
根据本公开实施例，无机电解液包括第一金属盐和水，其中，第一金属盐包括锂盐、钠盐、钾盐、镁盐、钙盐、铝盐中的一种或多种。According to an embodiment of the present disclosure, the inorganic electrolyte solution includes a first metal salt and water, wherein the first metal salt includes one or more of lithium salt, sodium salt, potassium salt, magnesium salt, calcium salt, and aluminum salt.
根据本公开实施例，有机电解液包括第二金属盐和有机溶剂，其中，第二金属盐包括锂盐、钾盐、钠盐中的一种或多种。According to an embodiment of the present disclosure, the organic electrolytic solution includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of lithium salt, potassium salt, and sodium salt.
本公开实施例中，锂盐包括但不限于LiPF 6、LiClO 4、LiTFSI、Li 2SO 4、LiBF 4、LiBOB、Li 2CO 3、LiHCO 3、LiAc、LiNO 3、LiBH 4。 In the embodiments of the present disclosure, lithium salts include but are not limited to LiPF 6 , LiClO 4 , LiTFSI, Li 2 SO 4 , LiBF 4 , LiBOB, Li 2 CO 3 , LiHCO 3 , LiAc, LiNO 3 , LiBH 4 .
本公开实施例中，钠盐包括但不限于NaClO 4、NaBF 4、NaPF 6、NaBOB、Na 2CO 3、NaHCO 3、NaNO 3、NaBH 4。 In the embodiments of the present disclosure, sodium salts include but are not limited to NaClO 4 , NaBF 4 , NaPF 6 , NaBOB, Na 2 CO 3 , NaHCO 3 , NaNO 3 , and NaBH 4 .
本公开实施例中，钾盐包括但不限于KClO 4、KBF 4、KPF 6、KBOB、K 2CO 3、KNO 3、KHCO 3、K 2SO 4、KBH 4。 In the embodiments of the present disclosure, potassium salts include but are not limited to KClO 4 , KBF 4 , KPF 6 , KBOB, K 2 CO 3 , KNO 3 , KHCO 3 , K 2 SO 4 , and KBH 4 .
本公开实施例中，镁盐包括但不限于MgCl 2、MgF 2、MgCO 3、MgSO 4、Mg(Ac) 2、Mg(ClO 4) 2、Mg(NO 3) 2。 In the embodiments of the present disclosure, magnesium salts include but are not limited to MgCl 2 , MgF 2 , MgCO 3 , MgSO 4 , Mg(Ac) 2 , Mg(ClO 4 ) 2 , and Mg(NO 3 ) 2 .
本公开实施例中，钙盐包括但不限于CaCl 2、CaF 2、CaCO 3、CaSO 4、Ca(OCl) 2、CaHPO 4、Ca(H 2PO 4) 2、Ca 3(PO 4) 2、Ca(NO 3) 2。 In the embodiments of the present disclosure, calcium salts include but are not limited to CaCl 2 , CaF 2 , CaCO 3 , CaSO 4 , Ca(OCl) 2 , CaHPO 4 , Ca(H 2 PO 4 ) 2 , Ca 3 (PO 4 ) 2 , Ca(NO 3 ) 2 .
本公开实施例中，铝盐包括但不限于AlCl 3、AlF 3、AlH(CO 3) 2、Al 2(SO 4) 3、AlPO 4、Al(NO 3) 3。 In the embodiments of the present disclosure, aluminum salts include but are not limited to AlCl 3 , AlF 3 , AlH(CO 3 ) 2 , Al 2 (SO 4 ) 3 , AlPO 4 , Al(NO 3 ) 3 .
本公开实施例中，无机电解液包括但不限于纯水溶液，还包括凝胶水溶液和金属离子浓度大于60％的高浓度水溶液。In the embodiments of the present disclosure, the inorganic electrolyte includes but is not limited to pure aqueous solution, and also includes gel aqueous solution and high-concentration aqueous solution with metal ion concentration greater than 60%.
本公开实施例中，无机电解液包括但不限于酸性溶液、中性溶液、碱性溶液。当无机电解液为碱性溶液时，无机电解液中还包括金属氢氧化物，例如：LiOH、NaOH、KOH、Mg(OH) 2、Al(OH) 3。 In the embodiments of the present disclosure, the inorganic electrolyte includes but not limited to acidic solution, neutral solution, and alkaline solution. When the inorganic electrolyte is an alkaline solution, the inorganic electrolyte also includes metal hydroxides, such as LiOH, NaOH, KOH, Mg(OH) 2 , Al(OH) 3 .
根据本公开实施例，有机溶剂包括乙腈、四氢呋喃、乙烯碳酸酯、丙烯碳酸酯、二乙基碳酸酯、二甲基碳酸酯、二甲基亚砜中的一种或多种。According to an embodiment of the present disclosure, the organic solvent includes one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, and dimethyl sulfoxide.
根据本公开实施例，固态电解质包括第一固态电解质、第二固态电解质中的一种或两种。According to an embodiment of the present disclosure, the solid electrolyte includes one or both of the first solid electrolyte and the second solid electrolyte.
根据本公开实施例，第一固态电解质包括非晶态硫化物型固态电解质、钙钛矿型固态电解质、钠超导型固态电解质、锂超导型固态电解质、石榴石型固态电解质、层状锂型固态电解质、玻璃-陶瓷固态电解质中的一种或多种。According to an embodiment of the present disclosure, the first solid electrolyte includes an amorphous sulfide solid electrolyte, a perovskite solid electrolyte, a sodium superconducting solid electrolyte, a lithium superconducting solid electrolyte, a garnet solid electrolyte, a layered lithium One or more of type solid electrolyte, glass-ceramic solid electrolyte.
本公开实施例中，非晶态硫化物型固态电解质包括但不限于Li 10GeP 2S 12、钙钛矿(Perovskite)型固态电解质包括但不限于Li 0.38Sr 0.44Ta 0.7Hf 0.3O 2.95F 0.05、钠超导(NASICON)型固态电解质包括但不限于LiZr 2(PO 4) 3、石榴石(Garnet)型固态电解质包括但不限于Li 7La 3Zr 2O 12、层状锂型固态电解质包括但不限于Li 3N、玻璃-陶瓷固态电解质包括但不限于Li 2.99Ca 0.005OCl。 In the embodiment of the present disclosure, the amorphous sulfide type solid electrolyte includes but not limited to Li 10 GeP 2 S 12 , the perovskite (Perovskite) type solid electrolyte includes but not limited to Li 0.38 Sr 0.44 Ta 0.7 Hf 0.3 O 2.95 F 0.05 , sodium superconducting (NASICON) type solid electrolyte including but not limited to LiZr 2 (PO 4 ) 3 , garnet (Garnet) type solid electrolyte including but not limited to Li 7 La 3 Zr 2 O 12 , layered lithium type solid electrolyte including But not limited to Li 3 N, glass-ceramic solid electrolytes include but not limited to Li 2.99 Ca 0.005 OCl.
根据本公开实施例，第二固态电解质包括聚氧化乙烯、聚丙烯晴、聚甲基丙烯酸甲酯、聚偏氟乙烯中的一种或多种。According to an embodiment of the present disclosure, the second solid electrolyte includes one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride.
本公开还提供了制备上述金属-氢气电池的方法，包括：在常温常压空气环境下，将正极活性物质涂布在电极材料上制备正极极片，将正极极片与无机电解液接触，完成氢气电极的制备。在无水无氧环境下，将金属电极与有机电解液接触，完成金属电极的制备。在无机电解液与有机电解液之间加入固态电解质作为隔膜。将氢气电极、金属电极、隔膜组装在电池装置中，并向电池装置中充入氢气，完成金属-氢气电池的制备。The present disclosure also provides a method for preparing the above-mentioned metal-hydrogen battery, which includes: coating the positive electrode active material on the electrode material to prepare the positive electrode sheet under normal temperature and normal pressure air environment, and contacting the positive electrode sheet with the inorganic electrolyte to complete Preparation of the hydrogen electrode. In an anhydrous and oxygen-free environment, the metal electrode is contacted with an organic electrolyte to complete the preparation of the metal electrode. A solid electrolyte is added between the inorganic electrolyte and the organic electrolyte as a diaphragm. Assemble the hydrogen electrode, the metal electrode and the separator in the battery device, and fill the battery device with hydrogen to complete the preparation of the metal-hydrogen battery.
下面分别以锂离子-氢气电池、钠金属-氢气电池、钾金属-氢气电池、钙金属-氢气电池、镁金属-氢气电池、铝金属-氢气电池、锂铝金属-氢气电池、掺杂锂铝合金金属-氢气电池为例，对本公开进行详细说明。The following are lithium-ion-hydrogen batteries, sodium metal-hydrogen batteries, potassium metal-hydrogen batteries, calcium metal-hydrogen batteries, magnesium metal-hydrogen batteries, aluminum metal-hydrogen batteries, lithium-aluminum metal-hydrogen batteries, and doped lithium-aluminum batteries. The alloy metal-hydrogen battery is taken as an example to describe the present disclosure in detail.
下述实施例1～8中的电池组装结构均如图1所示，自上至下依次包括氢气1、正极活性物质2、无机电解质3、固态电解质4、有机电解质5、金属负极6。The battery assembly structures in the following Examples 1-8 are all shown in Figure 1, including hydrogen gas 1, positive electrode active material 2, inorganic electrolyte 3, solid electrolyte 4, organic electrolyte 5, and metal negative electrode 6 from top to bottom.
实施例1Example 1
常温常压空气环境下，称取一定质量的Li 2SO 4充分溶解于去离子水混合配置2mol/L的Li 2SO 4水溶液，以NASICON-型的LiZr 2(PO 4) 3作为固态电解质材料。以NASICON-型的LiZr 2(PO 4) 3作为固态电解质材料，以高电压(3.04V)的锂金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, weigh a certain mass of Li 2 SO 4 and fully dissolve it in deionized water to mix and prepare a 2mol/L Li 2 SO 4 aqueous solution, using NASICON-type LiZr 2 (PO 4 ) 3 as a solid electrolyte material . NASICON-type LiZr 2 (PO 4 ) 3 is used as solid electrolyte material, high voltage (3.04V) lithium metal is used as negative electrode material, 5% mass fraction of platinum carbon catalyst is used as active material of positive electrode, polyvinylidene fluoride is used Using N-methyl-pyrrolidone as a binder and N-methyl-pyrrolidone as a solvent, stir it into a uniform slurry, and then coat it on the gas conductive layer to make a positive electrode sheet.
在无水无氧的手套箱中，使用上述锂金属离子迁移NASICON-型的LiZr 2(PO 4) 3的固态电解质，滴加比例为0.4ml/g的电解液(1mol/L LiPF 6，溶剂为EC/DMC/EMC)以消除 界面电阻，与锂金属一起组装得到锂金属负极。在常温常压下，在正极片一侧，与吸附上述Li 2SO 4水溶液玻璃纤维隔膜得到正极一侧。将锂金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到锂金属-氢气电池。 In an anhydrous and oxygen-free glove box, use the above-mentioned lithium metal ion migration NASICON-type LiZr 2 (PO 4 ) 3 solid electrolyte, drop an electrolyte solution (1mol/L LiPF 6 , solvent EC/DMC/EMC) to eliminate interfacial resistance, assembled with lithium metal to obtain lithium metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned Li 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the lithium metal out of the glove box, quickly attach it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill the device with a certain amount of hydrogen to obtain a lithium metal-hydrogen gas Battery.
以500mA/g的充放电电流、2500mAh/g为指定容量对该电池进行循环测试，测试仪器为LAND电池测试***。测试结果如图2所示，图2中位于上方的曲线为充电曲线，位于下方的曲线为放电曲线，放电曲线的最高放电电压接近2.85V。The battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g. The test instrument is a LAND battery test system. The test results are shown in Figure 2. The upper curve in Figure 2 is the charging curve, and the lower curve is the discharging curve. The highest discharge voltage of the discharging curve is close to 2.85V.
实施例2Example 2
常温常压空气环境下，称取一定质量的Na 2SO 4充分溶解于去离子水混合配置2mol/L的Na 2SO 4水溶液，以NASICON-型的NaZr 2(PO 4) 3作为固态电解质材料。以NASICON-型的NaZr 2(PO 4) 3作为固态电解质材料，以高高电压(2.71V)的钠金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, take a certain mass of Na 2 SO 4 and fully dissolve it in deionized water to mix and prepare a 2mol/L Na 2 SO 4 aqueous solution, using NASICON-type NaZr 2 (PO 4 ) 3 as a solid electrolyte material . NASICON-type NaZr 2 (PO 4 ) 3 is used as solid electrolyte material, high-voltage (2.71V) sodium metal is used as negative electrode material, 5% mass fraction of platinum carbon catalyst is used as positive electrode active material, and polyvinylidene fluoride Ethylene is used as a binder and N-methyl-pyrrolidone is used as a solvent. After being stirred into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet.
在无水无氧的手套箱中，使用上述钠金属离子迁移NASICON-型的NaZr 2(PO 4) 3的固态电解质，滴加比例为0.4ml/g的电解液(1mol/L NaClO 4，溶剂为EC/DMC/EMC)以消除界面电阻，与钠金属一起组装得到钠金属负极。在常温常压下，在正极片一侧，与吸附上述Na 2SO 4水溶液玻璃纤维隔膜得到正极一侧。将钠金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到钠金属-氢气电池。 In a water-free and oxygen-free glove box, use the above-mentioned sodium metal ion migration NASICON-type NaZr 2 (PO 4 ) 3 solid electrolyte, drop an electrolyte solution (1mol/L NaClO 4 , solvent EC/DMC/EMC) to eliminate interfacial resistance, and assembled with sodium metal to obtain a sodium metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned Na 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the sodium metal out of the glove box, quickly stick it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill the device with a certain amount of hydrogen to obtain sodium metal-hydrogen Battery.
以500mA/g的充放电电流、2500mAh/g为指定容量对该电池进行循环测试，测试仪器为LAND电池测试***。测试结果如图3所示，图3中位于上方的曲线为充电曲线，位于下方的曲线为放电曲线，放电曲线的最高放电电压接近2.5V。The battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g. The test instrument is a LAND battery test system. The test results are shown in Figure 3. The upper curve in Figure 3 is the charging curve, and the lower curve is the discharging curve. The highest discharge voltage of the discharging curve is close to 2.5V.
实施例3Example 3
常温常压空气环境下，称取一定质量的K 2SO 4充分溶解于去离子水混合配置2mol/L的K 2SO 4水溶液，以K 2PInS 4作为固态电解质材料，以高电压(2.92V)的钾金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, take a certain mass of K 2 SO 4 and fully dissolve it in deionized water to mix and prepare a 2mol/L K 2 SO 4 aqueous solution, use K 2 PInS 4 as a solid electrolyte material, and use a high voltage (2.92V ) of potassium metal as the negative electrode material, 5% mass fraction of platinum carbon catalyst as the active material of the positive electrode, with polyvinylidene fluoride as the binder, N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, coating Distributed on the gas conductive layer to make a positive pole piece.
在无水无氧的手套箱中，使用上述钾金属离子迁移K 2PInS 4的固态电解质，滴加比例为0.4ml/g的电解液(1mol/L KClO 4，溶剂为EC/DMC/EMC)以消除界面电阻，与钾金属一起组装得到钾金属负极。在常温常压下，在正极片一侧，与吸附上述K 2SO 4水溶液玻璃纤维隔膜得到正极一侧。将钾金属负极一侧从手套箱中取出后，快速与正极一侧 贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到钾金属-氢气电池。 In an anhydrous and oxygen-free glove box, use the above-mentioned potassium metal ion migration K 2 PInS 4 solid electrolyte, drop an electrolyte solution (1mol/L KClO 4 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g In order to eliminate the interfacial resistance, it is assembled with potassium metal to obtain a potassium metal anode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned K 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the potassium metal negative electrode side out of the glove box, quickly stick it to the positive electrode side and put it into a special battery device that can accommodate a certain volume of hydrogen gas, and then fill a certain amount of hydrogen gas into the device to obtain potassium metal-hydrogen gas Battery.
以500mA/g的充放电电流、2500mAh/g为指定容量对该电池进行循环测试，测试仪器为LAND电池测试***。测试结果如图4所示，图4中位于上方的曲线为充电曲线，位于下方的曲线为放电曲线，放电曲线的最高放电电压接近2.7V。The battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g. The test instrument is a LAND battery test system. The test results are shown in Figure 4. The upper curve in Figure 4 is the charging curve, and the lower curve is the discharge curve. The highest discharge voltage of the discharge curve is close to 2.7V.
实施例4Example 4
常温常压空气环境下，称取一定质量的CaCl 2充分溶解于去离子水混合配置2mol/L的CaCl 2水溶液，以含CaCl 2盐的PEO聚合物作为固态电解质材料，以高电压(2.87V)的钙金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and normal pressure air environment, take a certain mass of CaCl2 and fully dissolve it in deionized water to mix and configure a 2mol/L CaCl2 aqueous solution, use the PEO polymer containing CaCl2 salt as the solid electrolyte material, and use a high voltage (2.87V ) of calcium metal as the negative electrode material, 5% mass fraction of platinum carbon catalyst as the active material of the positive electrode, with polyvinylidene fluoride as the binder, N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, coating Distributed on the gas conductive layer to make a positive pole piece.
在无水无氧的手套箱中，使用上述钙金属离子迁移PEO聚合物固态电解质，滴加比例为0.4ml/g的电解液(1mol/L Ca(BF 4) 2，溶剂为EC/DMC/EMC)以消除界面电阻，与钙金属一起组装得到钙金属负极。在常温常压下，在正极片一侧，与吸附上述CaCl 2水溶液玻璃纤维隔膜得到正极一侧。将钙金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到钙金属-氢气电池。 In an anhydrous and oxygen-free glove box, using the above-mentioned calcium metal ion migration PEO polymer solid electrolyte, dropwise add the electrolyte solution (1mol/L Ca(BF 4 ) 2 at a ratio of 0.4ml/g, the solvent is EC/DMC/ EMC) to eliminate interfacial resistance, assembled with calcium metal to obtain calcium metal anode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned CaCl 2 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the calcium metal negative electrode side out of the glove box, quickly stick it to the positive electrode side and put it into a special battery device that can accommodate a certain volume of hydrogen gas, and then fill a certain amount of hydrogen gas into the device to obtain calcium metal-hydrogen gas Battery.
以500mA/g的充放电电流、2500mAh/g为指定容量对该电池进行循环测试，测试仪器为LAND电池测试***。测试结果如图5所示，图5中位于上方的曲线为充电曲线，位于下方的曲线为放电曲线，放电曲线的最高放电电压接近接近2.5V。The battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g. The test instrument is a LAND battery test system. The test results are shown in Figure 5. The upper curve in Figure 5 is the charging curve, and the lower curve is the discharge curve. The highest discharge voltage of the discharge curve is close to 2.5V.
实施例5Example 5
常温常压空气环境下，称取一定质量的MgCl 2充分溶解于去离子水混合配置2mol/L的MgCl 2水溶液，以含MgCl 2盐的PEO聚合物作为固态电解质材料，以高电压(2.37V)的钙金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and normal pressure air environment, take a certain amount of MgCl 2 and fully dissolve it in deionized water to mix and configure a 2mol/L MgCl 2 aqueous solution, use the PEO polymer containing MgCl 2 salt as the solid electrolyte material, and use a high voltage (2.37V ) of calcium metal as the negative electrode material, 5% mass fraction of platinum carbon catalyst as the active material of the positive electrode, with polyvinylidene fluoride as the binder, N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, coating Distributed on the gas conductive layer to make a positive pole piece.
在无水无氧的手套箱中，使用上述镁金属离子迁移PEO聚合物固态电解质，滴加比例为0.4ml/g的电解液(1mol/L MgCl 2，溶剂为EC/DMC/EMC)以消除界面电阻，与镁金属一起组装得到镁金属负极。在常温常压下，在正极片一侧，与吸附上述MgCl 2水溶液玻璃纤维隔膜得到正极一侧。将镁金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气， 得到镁金属-氢气电池。 In an anhydrous and oxygen-free glove box, use the above-mentioned magnesium metal ion migration PEO polymer solid electrolyte, drop an electrolyte solution (1mol/L MgCl 2 , solvent EC/DMC/EMC) with a ratio of 0.4ml/g to eliminate Interfacial resistance, assembled with magnesium metal to obtain magnesium metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned MgCl 2 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the magnesium metal out of the glove box, quickly attach it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill a certain amount of hydrogen into the device to obtain magnesium metal-hydrogen Battery.
以500mA/g的充放电电流、2500mAh/g为指定容量对该电池进行循环测试，测试仪器为LAND电池测试***。测试结果如图6所示，图6中位于上方的曲线为充电曲线，位于下方的曲线为放电曲线，放电曲线的最高放电电压接近2.3V。The battery is cycle tested with a charge and discharge current of 500mA/g and a specified capacity of 2500mAh/g. The test instrument is a LAND battery test system. The test results are shown in Figure 6. The upper curve in Figure 6 is the charging curve, and the lower curve is the discharging curve. The highest discharge voltage of the discharging curve is close to 2.3V.
综合上述实施例1-实施例5的循环测试结果，可以看出，采用本公开提供的金属-氢气电池，其放电平台均高于1.6V，最高可达到2.95V。Based on the above cycle test results of Examples 1 to 5, it can be seen that the discharge platform of the metal-hydrogen battery provided by the present disclosure is higher than 1.6V, and the highest can reach 2.95V.
实施例6Example 6
常温常压空气环境下，称取一定质量的AlCl 3充分溶解于去离子水混合配置2mol/L的AlCl 3水溶液，以含AlCl 3盐的PEO聚合物作为固态电解质材料，以高电压(1.67V)的铝金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, take a certain amount of AlCl 3 and fully dissolve it in deionized water to mix and configure a 2mol/L AlCl 3 aqueous solution, use the PEO polymer containing AlCl 3 salt as a solid electrolyte material, and use a high voltage (1.67V ) aluminum metal as the negative electrode material, 5% mass fraction of platinum carbon catalyst as the active material of the positive electrode, with polyvinylidene fluoride as the binder, N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, coating Distributed on the gas conductive layer to make a positive pole piece.
在无水无氧的手套箱中，使用上述铝金属离子迁移PEO聚合物固态电解质，滴加比例为0.4ml/g的电解液(1mol/L AlCl 3，溶剂为EC/DMC/EMC)以消除界面电阻，与铝金属一起组装得到铝金属负极。在常温常压下，在正极片一侧，与吸附上述AlCl 3水溶液玻璃纤维隔膜得到正极一侧。将铝金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到铝金属-氢气电池。 In an anhydrous and oxygen-free glove box, use the above-mentioned aluminum metal ion migration PEO polymer solid electrolyte, drop the electrolyte solution (1mol/L AlCl 3 , solvent is EC/DMC/EMC) with a ratio of 0.4ml/g to eliminate Interface resistance, assembled with aluminum metal to obtain aluminum metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned AlCl 3 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the aluminum metal out of the glove box, quickly attach it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill the device with a certain amount of hydrogen to obtain an aluminum metal-hydrogen gas Battery.
实施例7Example 7
常温常压空气环境下，称取一定质量的Li 2SO 4充分溶解于去离子水混合配置2mol/L的Li 2SO 4水溶液，以NASICON-型的LiZr 2(PO4) 3作为固态电解质材料。以NASICON-型的LiZr 2(PO4) 3作为固态电解质材料，以高电压(3.04V)的锂铝合金金属为负极材料，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, weigh a certain mass of Li 2 SO 4 and fully dissolve it in deionized water to prepare a 2mol/L Li 2 SO 4 aqueous solution, using NASICON-type LiZr 2 (PO4) 3 as a solid electrolyte material. NASICON-type LiZr 2 (PO4) 3 is used as solid electrolyte material, high voltage (3.04V) lithium aluminum alloy metal is used as negative electrode material, 5% mass fraction of platinum carbon catalyst is used as active material of positive electrode, polyvinylidene fluoride Ethylene is used as a binder and N-methyl-pyrrolidone is used as a solvent. After being stirred into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet.
在无水无氧的手套箱中，使用上述锂离子迁移NASICON-型的LiZr 2(PO4) 3的固态电解质，滴加比例为0.4ml/g的电解液(1mol/L LiPF 6，溶剂为EC/DMC/EMC)以消除界面电阻，与锂铝合金金属一起组装得到锂铝合金金属负极。在常温常压下，在正极片一侧，与吸附上述Li 2SO 4水溶液玻璃纤维隔膜得到正极一侧。将锂铝合金金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到锂铝合金金属-氢气电池。 In a water-free and oxygen-free glove box, use the above-mentioned lithium ion migration NASICON-type LiZr 2 (PO4) 3 solid electrolyte, drop the electrolyte solution (1mol/L LiPF 6 , solvent is EC /DMC/EMC) to eliminate interfacial resistance, and assembled with lithium aluminum alloy metal to obtain lithium aluminum alloy metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned Li 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the lithium-aluminum alloy metal out of the glove box, quickly attach it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill a certain amount of hydrogen into the device to obtain lithium aluminum Alloy metal-hydrogen battery.
实施例8Example 8
常温常压空气环境下，称取一定质量的Li 2SO 4充分溶解于去离子水混合配置2mol/L的Li2SO4水溶液，以NASICON-型的LiZr 2(PO4) 3作为固态电解质材料。以NASICON-型的LiZr 2(PO4) 3作为固态电解质材料，以高电压(3.04V)的Ba掺杂锂铝合金金属为负极材料，其中Ba含量为锂质量分数的1％，5％质量分数的铂碳催化剂为正极的活性物质，以聚偏氟乙烯为粘合剂、N-甲基-吡咯烷酮为溶剂，搅拌成均匀的浆料后，涂布在气体导电层上，制成正极极片。 Under normal temperature and pressure air environment, weigh a certain mass of Li 2 SO 4 and fully dissolve it in deionized water to prepare a 2mol/L Li2SO4 aqueous solution, using NASICON-type LiZr 2 (PO4) 3 as a solid electrolyte material. NASICON-type LiZr 2 (PO4) 3 is used as a solid electrolyte material, and a high-voltage (3.04V) Ba-doped lithium aluminum alloy metal is used as a negative electrode material, wherein the Ba content is 1% of the lithium mass fraction, 5% mass fraction The platinum carbon catalyst is the active material of the positive electrode, with polyvinylidene fluoride as the binder and N-methyl-pyrrolidone as the solvent, after stirring into a uniform slurry, it is coated on the gas conductive layer to make a positive electrode sheet .
在无水无氧的手套箱中，使用上述锂离子迁移NASICON-型的LiZr 2(PO4) 3的固态电解质，滴加比例为0.4ml/g的电解液(1mol/L LiPF 6，溶剂为EC/DMC/EMC)以消除界面电阻，与Ba掺杂锂铝合金金属一起组装得到锂铝合金金属负极。在常温常压下，在正极片一侧，与吸附上述Li 2SO 4水溶液玻璃纤维隔膜得到正极一侧。将Ba掺杂锂铝合金金属负极一侧从手套箱中取出后，快速与正极一侧贴紧并装入能够容纳一定体积氢气的特色电池装置中，然后在装置中充入一定量的氢气，得到Ba掺杂锂铝合金金属-氢气电池。 In a water-free and oxygen-free glove box, use the above-mentioned lithium ion migration NASICON-type LiZr 2 (PO4) 3 solid electrolyte, drop the electrolyte solution (1mol/L LiPF 6 , solvent is EC /DMC/EMC) to eliminate interfacial resistance, and assembled with Ba-doped lithium aluminum alloy metal to obtain lithium aluminum alloy metal negative electrode. Under normal temperature and pressure, on the side of the positive electrode sheet, absorb the above-mentioned Li 2 SO 4 aqueous solution glass fiber separator to obtain the positive electrode side. After taking the negative side of the Ba-doped lithium aluminum alloy metal out of the glove box, quickly stick it to the positive side and put it into a special battery device that can accommodate a certain volume of hydrogen, and then fill the device with a certain amount of hydrogen. A Ba-doped lithium aluminum alloy metal-hydrogen battery is obtained.
以上所述的具体实施例，对本公开的目的、技术方案和有益效果进行了进一步详细说明，应理解的是，以上所述仅为本公开的具体实施例而已，并不用于限制本公开，凡在本公开的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本公开的保护范围之内。The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present disclosure in detail. It should be understood that the above descriptions are only specific embodiments of the present disclosure, and are not intended to limit the present disclosure. Within the spirit and principles of the present disclosure, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present disclosure.

Claims (10)

  1. 一种金属-氢气电池，包括：正极、负极、电解液；其中，A metal-hydrogen battery, comprising: positive pole, negative pole, electrolyte; Wherein,
    所述正极包括氢气电极，其中，所述氢气电极包括含有正极活性物质的正极极片；The positive electrode includes a hydrogen electrode, wherein the hydrogen electrode includes a positive electrode sheet containing a positive active material;
    所述负极包括金属电极，其中，所述金属电极包括主金属和掺杂金属，其中，所述主金属包括Li、Na、K、Ca、Mg、Al中的一种或多种；所述掺杂金属包括Ni、Zn、Sr、Ba中的一种或多种；The negative electrode includes a metal electrode, wherein the metal electrode includes a main metal and a doped metal, wherein the main metal includes one or more of Li, Na, K, Ca, Mg, Al; The heterometal includes one or more of Ni, Zn, Sr, Ba;
    所述电解液包括正极侧的无机电解液、负极侧的有机电解液和分离所述无机电解液和所述有机电解液的固态电解质。The electrolytic solution includes an inorganic electrolytic solution on the positive side, an organic electrolytic solution on the negative side, and a solid electrolyte separating the inorganic electrolytic solution and the organic electrolytic solution.
  2. 根据权利要求1所述的电池，其中，所述掺杂金属的摩尔含量为所述主金属摩尔含量的0.01～10％。The battery according to claim 1, wherein the molar content of the doping metal is 0.01-10% of the molar content of the main metal.
  3. 根据权利要求1所述的电池，其中，所述正极活性物质包括第一金属催化剂、第二金属催化剂、第三金属催化剂、碳材料中的一种或多种。The battery according to claim 1, wherein the positive electrode active material comprises one or more of a first metal catalyst, a second metal catalyst, a third metal catalyst, and a carbon material.
  4. 根据权利要求3所述的电池，其中，The battery according to claim 3, wherein,
    所述第一金属催化剂包括Pt、Pd、Ir、Ru、PtNi、PtCo、PtMo、PtW、PtNiCo、PtNiMo、PdNi、PdCo、PdMo、PdW、PdNiCo、PdNiMo、IrNi、IrCo、IrMo、IrW、IrNiCo、IrNiMo、RuNi、RuCo、RuMo、RuW、RuNiCo、RuNiMo中的一种或多种；The first metal catalyst includes Pt, Pd, Ir, Ru, PtNi, PtCo, PtMo, PtW, PtNiCo, PtNiMo, PdNi, PdCo, PdMo, PdW, PdNiCo, PdNiMo, IrNi, IrCo, IrMo, IrW, IrNiCo, IrNiMo , one or more of RuNi, RuCo, RuMo, RuW, RuNiCo, RuNiMo;
    所述第二金属催化剂包括PtO 2、PtOH、PtC、IrO 2、IrC、IrN、IrS、IrP、RuO 2、RuC、RuN、RuS、RuP中的一种或多种； The second metal catalyst includes one or more of PtO 2 , PtOH, PtC, IrO 2 , IrC, IrN, IrS, IrP, RuO 2 , RuC, RuN, RuS, RuP;
    所述第三金属催化剂包括Ni、NiMo、NiCoMo、MoC、MoC 2、MoO 2、MoS 2、MoP、WC、WC 2、WO 2、WS 2、WP、NiN、NiS、NiP、NiPS中的一种或多种； The third metal catalyst includes one of Ni, NiMo, NiCoMo, MoC, MoC 2 , MoO 2 , MoS 2 , MoP, WC, WC 2 , WO 2 , WS 2 , WP, NiN, NiS, NiP, NiPS or more;
    所述碳材料包括微米球、纳米球、微米颗粒、纳米颗粒、微米片、纳米片、微米线、纳米线、微米管、纳米管中的一种或多种。The carbon material includes one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, and nanotubes.
  5. 根据权利要求1所述的电池，所述无机电解液包括第一金属盐和水，其中，所述第一金属盐包括锂盐、钠盐、钾盐、镁盐、钙盐、铝盐中的一种或多种。The battery according to claim 1, wherein the inorganic electrolyte comprises a first metal salt and water, wherein the first metal salt comprises lithium salts, sodium salts, potassium salts, magnesium salts, calcium salts, and aluminum salts one or more.
  6. 根据权利要求1所述的电池，所述有机电解液包括第二金属盐和有机溶剂，其中，所述第二金属盐包括锂盐、钾盐、钠盐中的一种或多种。The battery according to claim 1, wherein the organic electrolytic solution includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of lithium salt, potassium salt, and sodium salt.
  7. 根据权利要求6所述的电池，所述有机溶剂包括乙腈、四氢呋喃、乙烯碳酸酯、丙烯碳酸酯、二乙基碳酸酯、二甲基碳酸酯、二甲基亚砜中的一种或多种。The battery according to claim 6, wherein the organic solvent comprises one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate, and dimethyl sulfoxide .
  8. 根据权利要求1所述的电池，所述固态电解质包括第一固态电解质、第二固态电解质中的一种或两种。The battery according to claim 1, the solid electrolyte comprises one or both of the first solid electrolyte and the second solid electrolyte.
  9. 根据权利要求8所述的电池，其中，The battery according to claim 8, wherein,
    所述第一固态电解质包括非晶态硫化物型固态电解质、钙钛矿型固态电解质、钠超导型固态电解质、锂超导型固态电解质、石榴石型固态电解质、层状锂型固态电解质、玻璃-陶瓷固态电解质中的一种或多种；The first solid electrolyte includes an amorphous sulfide solid electrolyte, a perovskite solid electrolyte, a sodium superconducting solid electrolyte, a lithium superconducting solid electrolyte, a garnet solid electrolyte, a layered lithium solid electrolyte, One or more of glass-ceramic solid electrolytes;
    所述第二固态电解质包括聚氧化乙烯、聚丙烯晴、聚甲基丙烯酸甲酯、聚偏氟乙烯中的一种或多种。The second solid electrolyte includes one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, and polyvinylidene fluoride.
  10. 一种制备权利要求1～9任意一项所述电池的方法，包括：A method for preparing a battery according to any one of claims 1 to 9, comprising:
    在常温常压空气环境下，将正极活性物质涂布在电极材料上制备正极极片，将所述正极极片与无机电解液接触，完成氢气电极的制备；In an air environment at normal temperature and pressure, the positive electrode active material is coated on the electrode material to prepare the positive electrode sheet, and the positive electrode sheet is contacted with the inorganic electrolyte to complete the preparation of the hydrogen electrode;
    在无水无氧环境下，将金属电极与有机电解液接触，完成金属电极的制备；In an anhydrous and oxygen-free environment, contact the metal electrode with the organic electrolyte to complete the preparation of the metal electrode;
    在所述无机电解液与所述有机电解液之间加入固态电解质作为隔膜；adding a solid electrolyte between the inorganic electrolyte and the organic electrolyte as a separator;
    将所述氢气电极、所述金属电极、所述隔膜组装在电池装置中，并向所述电池装置中充入氢气，完成金属-氢气电池的制备。The hydrogen electrode, the metal electrode, and the diaphragm are assembled in a battery device, and hydrogen is charged into the battery device to complete the preparation of a metal-hydrogen battery.
PCT/CN2021/096432 2021-05-27 2021-05-27 Metal-hydrogen battery and preparation method therefor WO2022246747A1 (en)

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CN110612636A (en) * 2017-03-10 2019-12-24 Ineova 株式会社 Metal cathode battery
CN111033883A (en) * 2017-08-11 2020-04-17 里兰斯坦福初级大学理事会 Metal hydrogen battery for large-scale energy storage
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US5376475A (en) * 1994-03-16 1994-12-27 Ovonic Battery Company, Inc. Aqueous lithium-hydrogen ion rechargeable battery
US20100221596A1 (en) * 2009-02-06 2010-09-02 Huggins Robert A Systems, methods of manufacture and use involving lithium and/or hydrogen for energy-storage applications
CN110612636A (en) * 2017-03-10 2019-12-24 Ineova 株式会社 Metal cathode battery
CN111033883A (en) * 2017-08-11 2020-04-17 里兰斯坦福初级大学理事会 Metal hydrogen battery for large-scale energy storage
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