CN113328177A - Metal-hydrogen battery and preparation method thereof - Google Patents
Metal-hydrogen battery and preparation method thereof Download PDFInfo
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- CN113328177A CN113328177A CN202110588012.0A CN202110588012A CN113328177A CN 113328177 A CN113328177 A CN 113328177A CN 202110588012 A CN202110588012 A CN 202110588012A CN 113328177 A CN113328177 A CN 113328177A
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Abstract
The present disclosure provides a metal-hydrogen battery and a method for manufacturing the same, wherein the metal-hydrogen battery includes: a positive electrode, a negative electrode, and an electrolyte; the positive electrode comprises a hydrogen electrode, wherein the hydrogen electrode comprises a positive pole piece containing a positive active material. The cathode comprises a metal electrode, wherein the metal electrode comprises a main metal and a doped metal, wherein the main metal comprises one or more of Li, Na, K, Ca, Mg and Al; the doped metal comprises one or more of Ni, Zn, Sr and Ba. The electrolyte includes an inorganic electrolyte on the positive electrode side, an organic electrolyte on the negative electrode side, and a solid electrolyte separating the inorganic electrolyte and the organic electrolyte.
Description
Technical Field
The disclosure belongs to the technical field of electrochemistry, and particularly relates to a metal-hydrogen battery and a preparation method thereof.
Background
With the rapid development of the global information age, the demand for energy storage devices is rapidly increasing. In the related technology, the nickel-hydrogen battery with higher energy density and long-term stability is obtained by utilizing the excellent characteristics of the hydrogen electrode and matching with the nickel anode. The nickel-hydrogen battery energy storage technology is applied to aerospace vehicles and satellites, and the service life of the nickel-hydrogen battery energy storage technology exceeds fifteen years. Hydrogen gas, which is the currently known substance with the lightest relative molecular mass, has high theoretical capacity, is green and environment-friendly, has abundant resources, and widely exists in the universe, and hydrogen energy is regarded as one of clean energy sources with development potential in the world. In addition, the excellent bifunctional catalyst is adopted to catalyze the oxidation and reduction reactions of hydrogen, and the high capacity, low overpotential and stable service life are shown. Thus, high energy and power densities and long operating life can be achieved with hydrogen as the electrode of the cell. However, the conventional nickel-hydrogen battery is limited by the limited voltage window of the aqueous electrolyte, the discharge plateau is only 1.2V, and the catalyst is expensive, which prevents the wide application thereof.
Disclosure of Invention
In view of the above, the present disclosure provides a metal-hydrogen battery and a method for manufacturing the same, which are intended to at least partially solve the above technical problems.
As one aspect of the present disclosure, the present disclosure provides a metal-hydrogen battery including: a positive electrode, a negative electrode, and an electrolyte; the positive electrode comprises a hydrogen electrode, wherein the hydrogen electrode comprises a positive pole piece containing a positive active substance. The cathode comprises a metal electrode, wherein the metal electrode comprises a main metal and a doped metal, wherein the main metal comprises one or more of Li, Na, K, Ca, Mg and Al; the doped metal comprises one or more of Ni, Zn, Sr and Ba. The electrolyte includes an inorganic electrolyte on the positive electrode side, an organic electrolyte on the negative electrode side, and a solid electrolyte separating the inorganic electrolyte and the organic electrolyte.
According to the embodiment of the disclosure, the molar content of the doping metal is 0.01-10% of the molar content of the main metal.
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.
According to an embodiment of the present disclosure, the first metal catalyst includes one or more of 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, runio, RuNiMo.
According to an embodiment of the disclosure, the second metal catalyst comprises PtO2、PtOH、PtC、IrO2、IrC、IrN、IrS、IrP、RuO2One or more of RuC, RuN, RuS and RuP;
according to an embodiment of the present disclosure, the third metal catalyst includes Ni, NiMo, NiCoMo, MoC2、MoO2、MoS2、MoP、WC、WC2、WO2、WS2One or more of WP, NiN, NiS, NiP and NiPS;
according to an embodiment of the present disclosure, the carbon material comprises one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, nanotubes.
According to an embodiment of the present disclosure, the inorganic electrolyte includes a first metal salt and water, wherein the first metal salt includes one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, and an aluminum salt.
According to an embodiment of the present disclosure, the organic electrolyte includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of a lithium salt, a potassium salt, and a sodium salt.
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 sulfoxide.
According to an embodiment of the present disclosure, the solid electrolyte includes one or both of a first solid electrolyte, a second solid electrolyte.
According to an embodiment of the present disclosure, the first solid-state electrolyte includes one or more of an amorphous sulfide-type solid-state electrolyte, a perovskite-type solid-state electrolyte, a sodium superconducting-type solid-state electrolyte, a lithium superconducting-type solid-state electrolyte, a garnet-type solid-state electrolyte, a layered lithium-type solid-state electrolyte, a glass-ceramic solid-state electrolyte.
According to an embodiment of the present disclosure, the second solid-state electrolyte comprises one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride.
As another aspect of the present disclosure, the present disclosure also provides a method of preparing the above metal-hydrogen battery, comprising: and coating the positive active substance on an electrode material to prepare a positive pole piece under the air environment of normal temperature and normal pressure, and contacting the positive pole piece with an inorganic electrolyte to finish the preparation of the hydrogen electrode. And contacting the metal electrode with organic electrolyte under an anhydrous and oxygen-free environment to finish the preparation of the metal electrode. Solid electrolyte is added between the inorganic electrolyte and the organic electrolyte to be used as a diaphragm. And assembling the hydrogen electrode, the metal electrode and the diaphragm in a battery device, and filling hydrogen into the battery device to finish the preparation of the metal-hydrogen battery.
The metal-hydrogen battery related to the present disclosure uses the hydrogen electrode as the positive electrode, uses the metal electrode of low potential metal as the negative electrode, and because the electrode potentials of the metal electrode and the hydrogen electrode are both higher than 1.6V, the metal-hydrogen battery can obtain a working voltage higher than 1.6V, and breaks through the voltage window limitation that the working voltage of the existing hydrogen battery system is lower than 1.4V.
Drawings
Fig. 1 schematically shows a schematic view of the structure of a metal-hydrogen battery;
fig. 2 schematically shows a charging curve of the lithium metal-hydrogen battery prepared in example 1 for the first 2 times;
fig. 3 schematically shows the first charge and discharge curves of the sodium metal-hydrogen battery prepared in example 2 subjected to a cycle test at a charge and discharge current of 500mA/g and a capacity of 2500 mAh/g;
fig. 4 schematically shows a first charge and discharge curve of a cycle test of the potassium metal-hydrogen battery prepared in example 3 at a charge and discharge current of 500mA/g and a capacity of 2500 mAh/g;
fig. 5 schematically shows a first charge and discharge curve of a cycle test of the prepared calcium metal-hydrogen battery of example 4 with a charge and discharge current of 500mA/g and a capacity of 2500mAh/g as specified;
fig. 6 schematically shows a first charge and discharge curve of a cycle test of the prepared magnesium metal-hydrogen battery of example 5 at a charge and discharge current of 500mA/g and a capacity of 2500 mAh/g.
Detailed Description
For the purpose of promoting a better understanding of the objects, aspects and advantages of the present disclosure, reference is made to the following detailed description taken in conjunction with the accompanying drawings.
In recent years, although a discharge platform of a novel manganese-hydrogen battery system, a water system iron-hydrogen battery, an acid lead-hydrogen battery, a neutral manganese-hydrogen battery, an alkaline nickel-hydrogen battery system and the like can be improved to a certain extent by selecting an electrode material with a higher potential, the problem of limitation of a voltage window of a water system electrolyte is not really changed, so that the discharge voltage of the current hydrogen battery is difficult to break through 1.6V (generally lower than 1.4V), and the large-scale application of the hydrogen battery is limited. Therefore, expanding the voltage window of hydrogen batteries by developing new battery systems is very critical for constructing energy storage systems with high energy density.
The present disclosure provides a metal-hydrogen battery comprising: a positive electrode, a negative electrode, and an electrolyte; the positive electrode comprises a hydrogen electrode, wherein the hydrogen electrode comprises a positive pole piece containing a positive active substance. The cathode comprises a metal electrode, wherein the metal electrode comprises a main metal and a doped metal, wherein the main metal comprises one or more of Li, Na, K, Ca, Mg and Al; the doped metal comprises one or more of Ni, Zn, Sr and Ba. The electrolyte includes an inorganic electrolyte on the positive electrode side, an organic electrolyte on the negative electrode side, and a solid electrolyte separating the inorganic electrolyte and the organic electrolyte.
In the embodiment of the disclosure, the hydrogen electrode is used as the anode, the metal electrode of low-potential metal is used as the cathode, the combination of inorganic electrolyte and organic electrolyte is used as the electrolyte, and 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, and the limitation of a voltage window that the working voltage of the existing hydrogen battery system is lower than 1.4V is broken through.
In the embodiments of the present disclosure, the metal electrode includes, but is not limited to, a main metal and a doped metal, and further includes a mixture of the main metal and the nanocarbon material. The nano carbon material can adopt one or more of nanospheres, nanoparticles, nanosheets, nanowires and nanotubes.
According to the embodiment of the disclosure, the molar content of the doping metal is 0.01-10% of the molar content of the main metal. For example: 0.01%, 1%, 3%, 5%, 8%, 10%.
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.
According to an embodiment of the present disclosure, the first metal catalyst includes one or more of 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, runio, RuNiMo.
According to an embodiment of the disclosure, the second metal catalyst comprises PtO2、PtOH、PtC、IrO2、IrC、IrN、IrS、IrP、RuO2One or more of RuC, RuN, RuS and RuP;
according to an embodiment of the present disclosure, the third metal catalyst includes Ni, NiMo, NiCoMo, MoC2、MoO2、MoS2、MoP、WC、WC2、WO2、WS2One or more of WP, NiN, NiS, NiP and NiPS;
according to an embodiment of the present disclosure, the carbon material comprises one or more of microspheres, nanospheres, microparticles, nanoparticles, microsheets, nanosheets, microwires, nanowires, microtubes, nanotubes.
According to an embodiment of the present disclosure, the inorganic electrolyte includes a first metal salt and water, wherein the first metal salt includes one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, and an aluminum salt.
According to an embodiment of the present disclosure, the organic electrolyte includes a second metal salt and an organic solvent, wherein the second metal salt includes one or more of a lithium salt, a potassium salt, and a sodium salt.
In embodiments of the present disclosure, the lithium salt includes, but is not limited to, LiPF6、LiClO4、LiTFSI、Li2SO4、LiBF4、LiBOB、Li2CO3、LiHCO3、LiAc、LiNO3、LiBH4。
In the disclosed embodiments, sodium salts include, but are not limited to, NaClO4、NaBF4、NaPF6、NaBOB、Na2CO3、NaHCO3、NaNO3、NaBH4。
In the disclosed embodiments, potassium salts include, but are not limited to, KClO4、KBF4、KPF6、KBOB、K2CO3、KNO3、KHCO3、K2SO4、KBH4。
In embodiments of the present disclosure, magnesium salts include, but are not limited to, MgCl2、MgF2、MgCO3、MgSO4、Mg(Ac)2、Mg(ClO4)2、Mg(NO3)2。
In the disclosed embodiments, the calcium salt includes, but is not limited to, CaCl2、CaF2、CaCO3、CaSO4、Ca(OCl)2、CaHPO4、Ca(H2PO4)2、Ca3(PO4)2、Ca(NO3)2。
In embodiments of the present disclosure, aluminum salts include, but are not limited to, AlCl3、AlF3、AlH(CO3)2、Al2(SO4)3、AlPO4、Al(NO3)3。
In the embodiment of the present disclosure, the inorganic electrolyte includes, but is not limited to, a pure water solution, and further includes a gel aqueous solution and a high-concentration aqueous solution having a metal ion concentration of more than 60%.
In the embodiments of the present disclosure, the inorganic electrolyte includes, but is not limited to, an acidic solution, a neutral solution, and an alkaline solution. When the inorganic electrolyte is an alkaline solution, the inorganic electrolyte further includes a metal hydroxide, for example: LiOH, NaOH, KOH, Mg (OH)2、Al(OH)3。
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 sulfoxide.
According to an embodiment of the present disclosure, the solid electrolyte includes one or both of a first solid electrolyte, a second solid electrolyte.
According to an embodiment of the present disclosure, the first solid-state electrolyte includes one or more of an amorphous sulfide-type solid-state electrolyte, a perovskite-type solid-state electrolyte, a sodium superconducting-type solid-state electrolyte, a lithium superconducting-type solid-state electrolyte, a garnet-type solid-state electrolyte, a layered lithium-type solid-state electrolyte, a glass-ceramic solid-state electrolyte.
In embodiments of the present disclosure, amorphous sulfide-type solid electrolytes include, but are not limited to, Li10GeP2S12Perovskite (Perovskite) type solid electrolytes include, but are not limited to, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05Sodium superconducting (NASICON) type solid electrolytes include, but are not limited to, LiZr2(PO4)3Garnet (Garnet) -type solid electrolytes include, but are not limited to, Li7La3Zr2O12Layered lithium type solid electrolytes include, but are not limited to, Li3N, glass-ceramic solid electrolytes include but are not limited to Li2.99Ca0.005OCl。
According to an embodiment of the present disclosure, the second solid-state electrolyte comprises one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polyvinylidene fluoride.
The present disclosure also provides a method of making the above metal-hydrogen battery, comprising: and coating the positive active substance on an electrode material to prepare a positive pole piece under the air environment of normal temperature and normal pressure, and contacting the positive pole piece with an inorganic electrolyte to finish the preparation of the hydrogen electrode. And contacting the metal electrode with organic electrolyte under an anhydrous and oxygen-free environment to finish the preparation of the metal electrode. Solid electrolyte is added between the inorganic electrolyte and the organic electrolyte to be used as a diaphragm. And assembling the hydrogen electrode, the metal electrode and the diaphragm in a battery device, and filling hydrogen into the battery device to finish the preparation of the metal-hydrogen battery.
The present disclosure will be described in detail below by taking a lithium ion-hydrogen battery, a sodium metal-hydrogen battery, a potassium metal-hydrogen battery, a calcium metal-hydrogen battery, a magnesium metal-hydrogen battery, an aluminum metal-hydrogen battery, a lithium aluminum metal-hydrogen battery, and a lithium-doped aluminum alloy metal-hydrogen battery as examples.
The battery assembly structures in the following examples 1 to 8 each include, as shown in fig. 1, a hydrogen gas 1, a positive electrode active material 2, an inorganic electrolyte 3, a solid electrolyte 4, an organic electrolyte 5, and a metal negative electrode 6 in this order from top to bottom.
Example 1
Weighing a certain mass of Li under the air environment of normal temperature and pressure2SO4Fully dissolved in deionized water to prepare 2mol/L Li2SO4Aqueous solution of NASICON-type LiZr2(PO4)3As a solid electrolyte material. LiZr in NASICON-type2(PO4)3As a solid electrolyte material, lithium metal with high voltage (3.04V) is used as a negative electrode material, 5% by mass of platinum carbon catalyst is used as an active material of a positive electrode, polyvinylidene fluoride is used as a binder, N-methyl-pyrrolidone is used as a solvent, and the mixture is stirred into uniform slurry and then coated on a gas conductive layer to prepare a positive electrode piece.
Using the above lithium metal ion transporting NASICON-type LiZr in a glove box without water and oxygen2(PO4)3The solid electrolyte of (2), an electrolyte (1mol/L LiPF) was added dropwise in a ratio of 0.4ml/g6And the solvent is EC/DMC/EMC) to eliminate interfacial resistance, and assembling the lithium metal anode together with the lithium metal. Adsorbing the Li on one side of the positive plate at normal temperature and normal pressure2SO4The positive side was obtained with an aqueous glass fiber separator. And taking one side of the lithium metal cathode out of the glove box, quickly attaching the lithium metal cathode to one side of the anode, putting the lithium metal cathode and the anode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the lithium metal-hydrogen battery.
The battery is subjected to cycle test by taking the charging and discharging current of 500mA/g and 2500mAh/g as the specified capacity, and the test instrument is a LAND battery test system. As shown in fig. 2, the upper curve in fig. 2 is a charging curve, the lower curve is a discharging curve, and the highest discharging voltage of the discharging curve is close to 2.85V.
Example 2
Weighing a certain mass of Na under the air environment of normal temperature and normal pressure2SO4Fully dissolved in deionized water to prepare 2mol/L Na2SO4Aqueous solution of NASICON-type NaZr2(PO4)3As a solid electrolyte material. NaZr in NASICON-type2(PO4)3As a solid electrolyte material, high-voltage (2.71V) sodium metal is used as a negative electrode material, 5 mass percent of platinum-carbon catalyst is used as an active substance of a positive electrode, polyvinylidene fluoride is used as a bonding agent, N-methyl-pyrrolidone is used as a solvent, and the mixture is stirred into uniform slurry and then coated on a gas conductive layer to prepare a positive electrode piece.
Using the above sodium metal ion transporting NASICON-type NaZr in a glove box without water and oxygen2(PO4)3The solid electrolyte of (2), an electrolyte (1mol/L NaClO) was added dropwise in a ratio of 0.4ml/g4The solvent is EC/DMC/EMC) to eliminate the interface resistance, and the sodium metal is assembled together to obtain the sodium metal cathode. Adsorbing the Na on one side of the positive plate at normal temperature and normal pressure2SO4The positive side was obtained with an aqueous glass fiber separator. And taking one side of the sodium metal cathode out of the glove box, quickly attaching the sodium metal cathode to one side of the anode, putting the sodium metal cathode and the anode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the sodium metal-hydrogen battery.
The battery is subjected to cycle test by taking the charging and discharging current of 500mA/g and 2500mAh/g as the specified capacity, and the test instrument is a LAND battery test system. The test results are shown in fig. 3, in which the upper curve in fig. 3 is a charging curve, the lower curve is a discharging curve, and the highest discharging voltage of the discharging curve is close to 2.5V.
Example 3
Weighing a certain mass of K under the air environment of normal temperature and normal pressure2SO4Fully dissolved in deionized water to prepare 2mol/L K2SO4Aqueous solution of K2PInS4As a solid electrolyte material, potassium metal with high voltage (2.92V) is used as a negative electrode material, 5% of platinum carbon catalyst by mass is used as an active substance of a positive electrode, polyvinylidene fluoride is used as a bonding agent, N-methyl-pyrrolidone is used as a solvent, and the mixture is stirred into uniform slurry and then coated on a gas conductive layer to prepare a positive electrode piece.
In a water-free and oxygen-free glove box, the potassium metal ion migration K is used2PInS4The solid electrolyte of (2), an electrolyte (1mol/L KClO) was added dropwise in a ratio of 0.4ml/g4And the solvent is EC/DMC/EMC) to eliminate the interface resistance, and the potassium metal anode is obtained by assembling the solvent and the potassium metal. Adsorbing the K on one side of the positive plate at normal temperature and normal pressure2SO4The positive side was obtained with an aqueous glass fiber separator. And taking out one side of the potassium metal cathode from the glove box, quickly attaching the potassium metal cathode to one side of the anode, putting the potassium metal cathode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the potassium metal-hydrogen battery.
The battery is subjected to cycle test by taking the charging and discharging current of 500mA/g and 2500mAh/g as the specified capacity, and the test instrument is a LAND battery test system. The test results are shown in fig. 4, in which the upper curve in fig. 4 is a charging curve, the lower curve is a discharging curve, and the highest discharging voltage of the discharging curve is close to 2.7V.
Example 4
Weighing a certain mass of CaCl under the air environment of normal temperature and normal pressure2Fully dissolved in deionized water to be mixed with 2mol/L CaCl2Aqueous solution of CaCl2The PEO polymer of the salt is used as a solid electrolyte material, calcium metal with high voltage (2.87V) is used as a negative electrode material, a platinum-carbon catalyst with the mass fraction of 5% is used as an active substance of a positive electrode, polyvinylidene fluoride is used as an adhesive, N-methyl-pyrrolidone is used as a solvent, the mixture is stirred into uniform slurry, and then the uniform slurry is coated on a gas conducting layer to prepare a positive electrode piece.
In a water-free and oxygen-free glove box, the calcium metal ion migration PEO polymer solid electrolyte is used, and the electrolyte with the proportion of 0.4ml/g (1 mol/L) is drippedCa(BF4)2And the solvent is EC/DMC/EMC) to eliminate the interface resistance, and the calcium metal anode is assembled together with calcium metal. Adsorbing the above CaCl on one side of the positive plate at normal temperature and normal pressure2The positive side was obtained with an aqueous glass fiber separator. And taking out one side of the calcium metal cathode from the glove box, quickly attaching the calcium metal cathode to one side of the anode, putting the calcium metal cathode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the calcium metal-hydrogen battery.
The battery is subjected to cycle test by taking the charging and discharging current of 500mA/g and 2500mAh/g as the specified capacity, and the test instrument is a LAND battery test system. The test results are shown in fig. 5, in which the upper curve in fig. 5 is a charging curve, the lower curve is a discharging curve, and the highest discharging voltage of the discharging curve is close to 2.5V.
Example 5
Weighing MgCl with a certain mass under the air environment of normal temperature and pressure2Fully dissolved in deionized water to prepare MgCl with the concentration of 2mol/L2Aqueous solution to contain MgCl2The PEO polymer of the salt is used as a solid electrolyte material, calcium metal with high voltage (2.37V) is used as a negative electrode material, a platinum-carbon catalyst with the mass fraction of 5% is used as an active substance of a positive electrode, polyvinylidene fluoride is used as an adhesive, N-methyl-pyrrolidone is used as a solvent, the mixture is stirred into uniform slurry, and then the uniform slurry is coated on a gas conducting layer to prepare a positive electrode piece.
In a water-free and oxygen-free glove box, the magnesium metal ion migration PEO polymer solid electrolyte is used, and electrolyte (1mol/L MgCl) with the proportion of 0.4ml/g is added dropwise2And the solvent is EC/DMC/EMC) to eliminate the interface resistance, and the magnesium metal negative electrode is obtained by assembling the solvent and the magnesium metal together. Adsorbing the MgCl on one side of the positive plate under normal temperature and normal pressure2The positive side was obtained with an aqueous glass fiber separator. And taking out one side of the magnesium metal cathode from the glove box, quickly attaching the magnesium metal cathode to one side of the anode, putting the magnesium metal cathode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the magnesium metal-hydrogen battery.
The battery is subjected to cycle test by taking the charging and discharging current of 500mA/g and 2500mAh/g as the specified capacity, and the test instrument is a LAND battery test system. As shown in fig. 6, the upper curve in fig. 6 is a charging curve, the lower curve is a discharging curve, and the highest discharging voltage of the discharging curve is close to 2.3V.
From the results of the cycle tests of the above examples 1 to 5, it can be seen that the discharge plateaus of the metal-hydrogen batteries provided by the present disclosure are all higher than 1.6V, and can reach 2.95V at most.
Example 6
Weighing AlCl with certain mass under the air environment of normal temperature and normal pressure3Fully dissolved in deionized water to prepare 2mol/L AlCl3Aqueous solution of AlCl3The PEO polymer of the salt is used as a solid electrolyte material, aluminum metal with high voltage (1.67V) is used as a negative electrode material, a platinum-carbon catalyst with the mass fraction of 5% is used as an active substance of a positive electrode, polyvinylidene fluoride is used as a binder, N-methyl-pyrrolidone is used as a solvent, the mixture is stirred into uniform slurry, and then the uniform slurry is coated on a gas conducting layer to prepare a positive electrode piece.
In a water-free and oxygen-free glove box, the aluminum metal ion migration PEO polymer solid electrolyte is used, and the electrolyte (1mol/L AlCl) with the proportion of 0.4ml/g is added dropwise3The solvent is EC/DMC/EMC) to eliminate the interface resistance, and the aluminum metal negative electrode is obtained by assembling the aluminum metal and the solvent together. Adsorbing the AlCl on one side of the positive plate at normal temperature and normal pressure3The positive side was obtained with an aqueous glass fiber separator. And taking out one side of the aluminum metal cathode from the glove box, quickly attaching the aluminum metal cathode to one side of the anode, putting the aluminum metal cathode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the aluminum metal-hydrogen battery.
Example 7
Weighing a certain mass of Li under the air environment of normal temperature and pressure2SO4Fully dissolved in deionized water to prepare 2mol/L Li2SO4Aqueous solution of NASICON-type LiZr2(PO4)3As a solid electrolyte material. LiZr in NASICON-type2(PO4)3As a solid electrolyte material, is highLithium-aluminum alloy metal with voltage (3.04V) is used as a negative electrode material, 5% of platinum-carbon catalyst in mass fraction is used as an active substance of a positive electrode, polyvinylidene fluoride is used as a binder, N-methyl-pyrrolidone is used as a solvent, and after being stirred into uniform slurry, the slurry is coated on a gas conducting layer to prepare a positive electrode piece.
Using the above LiZr of the lithium ion transport NASICON-type in a glove box free of water and oxygen2(PO4)3The solid electrolyte of (2), an electrolyte (1mol/L LiPF) was added dropwise in a ratio of 0.4ml/g6And the solvent is EC/DMC/EMC) to eliminate the interface resistance, and the lithium aluminum alloy metal negative electrode is obtained by assembling the lithium aluminum alloy metal and the solvent together. Adsorbing the Li on one side of the positive plate at normal temperature and normal pressure2SO4The positive side was obtained with an aqueous glass fiber separator. And taking one side of the lithium aluminum alloy metal cathode out of the glove box, quickly attaching the lithium aluminum alloy metal cathode to one side of the anode, placing the lithium aluminum alloy metal cathode into a special battery device capable of containing a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the lithium aluminum alloy metal-hydrogen battery.
Example 8
Weighing a certain mass of Li under the air environment of normal temperature and pressure2SO4Fully dissolved in deionized water to prepare 2mol/L Li2SO4 aqueous solution, and is prepared into NASICON-type LiZr2(PO4)3As a solid electrolyte material. LiZr in NASICON-type2(PO4)3As a solid electrolyte material, a high-voltage (3.04V) Ba-doped lithium aluminum alloy metal is used as a negative electrode material, wherein the content of Ba is 1% of the mass fraction of lithium, 5% of a platinum carbon catalyst is used as an active substance of a positive electrode, polyvinylidene fluoride is used as a bonding agent, N-methyl-pyrrolidone is used as a solvent, and after being stirred into uniform slurry, the slurry is coated on a gas conducting layer to prepare a positive electrode piece.
Using the above LiZr of the lithium ion transport NASICON-type in a glove box free of water and oxygen2(PO4)3The solid electrolyte of (2), an electrolyte (1mol/L LiPF) was added dropwise in a ratio of 0.4ml/g6The solvent is EC/DMC/EMC) to eliminate the interface resistance, and the Ba-doped lithium aluminum alloy metal is assembled together to obtain the lithium aluminum alloy metal cathode. At normal temperature and normal pressure, on the positive plate ISide, and adsorbing the above Li2SO4The positive side was obtained with an aqueous glass fiber separator. And taking one side of the Ba-doped lithium aluminum alloy metal cathode out of the glove box, quickly attaching the Ba-doped lithium aluminum alloy metal cathode to one side of the anode, placing the Ba-doped lithium aluminum alloy metal cathode into a special battery device capable of accommodating a certain volume of hydrogen, and then filling a certain amount of hydrogen into the device to obtain the Ba-doped lithium aluminum alloy metal-hydrogen battery.
The above-mentioned embodiments are intended to illustrate the objects, aspects and advantages of the present disclosure in further detail, and it should be understood that the above-mentioned embodiments are only illustrative of the present disclosure and are not intended to limit the present disclosure, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present disclosure should be included in the scope of the present disclosure.
Claims (10)
1. A metal-hydrogen battery comprising: a positive electrode, a negative electrode, and an electrolyte; wherein the content of the first and second substances,
the positive electrode comprises a hydrogen electrode, wherein the hydrogen electrode comprises a positive pole piece containing a positive active substance;
the negative electrode comprises a metal electrode, wherein the metal electrode comprises a main metal and a doped metal, wherein the main metal comprises one or more of Li, Na, K, Ca, Mg and Al; the doped metal comprises one or more of Ni, Zn, Sr and Ba;
the electrolyte includes an inorganic electrolyte on the positive electrode side, an organic electrolyte on the negative electrode side, and a solid electrolyte separating the inorganic electrolyte and the organic electrolyte.
2. The battery according to claim 1, wherein the molar content of the doping metal is 0.01 to 10% of the molar content of the main metal.
3. The battery according to claim 1, wherein 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.
4. The battery according to claim 3,
the first metal catalyst comprises one or more of 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 and RuNiMo;
the second metal catalyst comprises PtO2、PtOH、PtC、IrO2、IrC、IrN、IrS、IrP、RuO2One or more of RuC, RuN, RuS and RuP;
the third metal catalyst comprises Ni, NiMo, NiCoMo, MoC and MoC2、MoO2、MoS2、MoP、WC、WC2、WO2、WS2One or more of WP, NiN, NiS, NiP and NiPS;
the carbon material comprises one or more of microspheres, nanospheres, microparticles, nanoparticles, micron sheets, nanosheets, microwires, nanowires, microtubes and nanotubes.
5. The battery of claim 1, the inorganic electrolyte comprising a first metal salt and water, wherein the first metal salt comprises one or more of a lithium salt, a sodium salt, a potassium salt, a magnesium salt, a calcium salt, an aluminum salt.
6. The battery of claim 1, the organic electrolyte comprising a second metal salt and an organic solvent, wherein the second metal salt comprises one or more of a lithium salt, a potassium salt, and a sodium salt.
7. The battery of claim 6, the organic solvent comprising one or more of acetonitrile, tetrahydrofuran, ethylene carbonate, propylene carbonate, diethyl carbonate, dimethyl sulfoxide.
8. The battery of claim 1, the solid state electrolyte comprising one or both of a first solid state electrolyte, a second solid state electrolyte.
9. The battery according to claim 8,
the first solid electrolyte comprises one or more of amorphous sulfide type solid electrolyte, perovskite type solid electrolyte, sodium superconducting type solid electrolyte, lithium superconducting type solid electrolyte, garnet type solid electrolyte, layered lithium type solid electrolyte and glass-ceramic solid electrolyte;
the second solid electrolyte comprises one or more of polyethylene oxide, polyacrylonitrile, polymethyl methacrylate and polyvinylidene fluoride.
10. A method of making the battery of any one of claims 1-9, comprising:
coating a positive active substance on an electrode material to prepare a positive pole piece under the air environment of normal temperature and normal pressure, and contacting the positive pole piece with an inorganic electrolyte to finish the preparation of a hydrogen electrode;
under the anhydrous and oxygen-free environment, the metal electrode is contacted with the organic electrolyte to complete the preparation of the metal electrode;
adding a solid electrolyte as a diaphragm between the inorganic electrolyte and the organic electrolyte;
and assembling the hydrogen electrode, the metal electrode and the diaphragm in a battery device, and filling hydrogen into the battery device to finish the preparation of the metal-hydrogen battery.
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