CN111009653B - Preparation method of zinc cathode material of zinc-nickel secondary battery - Google Patents
Preparation method of zinc cathode material of zinc-nickel secondary battery Download PDFInfo
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- CN111009653B CN111009653B CN201911259501.0A CN201911259501A CN111009653B CN 111009653 B CN111009653 B CN 111009653B CN 201911259501 A CN201911259501 A CN 201911259501A CN 111009653 B CN111009653 B CN 111009653B
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/24—Alkaline accumulators
- H01M10/30—Nickel accumulators
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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
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- 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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Abstract
The invention discloses a preparation method of a zinc cathode material of a zinc-nickel secondary battery, which comprises the following specific steps: dissolving soluble zinc salt, soluble tin salt and soluble copper salt in deionized water, adding a precipitator for precipitation, then filtering, washing, drying, placing in a tubular furnace, heating to 700-1050 ℃ in inert atmosphere, keeping the temperature for 1-10 h, and cooling to room temperature along with the furnace to obtain Zn cathode material of the zinc-nickel secondary battery, wherein Zn contains Zn, sn and Cu x Cu y SnO 4 Crystal, the zinc-nickel secondary battery zinc cathode material Zn x Cu y SnO 4 The crystal is used as the cathode active substance or additive of the zinc-nickel secondary battery, can improve the power and specific energy performance of the zinc-nickel secondary battery, prevent the zinc cathode of the zinc-nickel secondary battery from expanding, falling off and dendritic crystal from growing, and further prolong the service life of the zinc-nickel secondary battery.
Description
Technical Field
The invention belongs to the technical field of preparation of zinc cathode materials of zinc-nickel secondary batteries, and particularly relates to a preparation method of a zinc cathode material of a zinc-nickel secondary battery.
Background
The currently available square secondary batteries mainly comprise lead-acid batteries, nickel-hydrogen batteries and lithium ion batteries, wherein the lead-acid batteries have low specific energy which can only reach 30 to 35Wh/Kg generally, the cycle life is about 300 to 350 times, longer charging time is needed, lead is toxic heavy metal, and the production process and recovery process can cause serious pollution to the environment if the lead is not properly treated, so the production and use of the lead-acid batteries are limited by countries in the world. The nickel-hydrogen battery has low working voltage, large self-discharge at high temperature, needs a large amount of rare earth raw materials, has high cost price, and is only suitable for being used as a power supply of small-sized electrical appliances at present. The specific energy of the lithium ion battery is relatively high, and the lithium ion battery can be charged and discharged by heavy current; however, the environment is easily polluted in the production and recovery processes, so-called environmental protection is only compared with that of a lead-acid battery, and because the lithium ion battery has a safety problem, especially has poorer safety performance in a high-capacity and high-voltage use environment, and meanwhile, a series of problems that the waste lithium iron phosphate, lithium manganate and other lithium ion batteries are difficult to recover, have pollution and have no recovery value and the like, the lithium ion battery has a great influence on the future human environment to a certain extent.
The traditional zinc-nickel battery cathode adopts zinc oxide powder with fine granularity as an active substance, zinc ions are easy to dissolve out in the discharge process of alkaline electrolyte, the zinc ions are deposited on the uneven convex part of the electrode surface to form dendrites in the charging process, and the dendrites penetrate through a diaphragm to cause short circuit of a positive electrode and a negative electrode, so that the battery fails. Although researchers have done a great deal of work in recent years trying to extend the cycle life of zinc-nickel batteries, current research work is primarily limited to zinc-nickel battery electrolytes and separators, and a small portion of the research work is seeking strategies for electrode additives. The problems of expansion, falling off, dendritic crystal growth and the like of the zinc cathode material of the zinc-nickel battery cannot be well solved by the conventional method.
Disclosure of Invention
The technical problem solved by the invention is to provide a preparation method of a zinc cathode material of a zinc-nickel secondary battery, the zinc cathode material of the zinc-nickel secondary battery prepared by the method effectively solves the problems of expansion, falling off, dendrite growth and the like of the zinc cathode of the zinc-nickel secondary battery, and simultaneously effectively prolongs the service life of the zinc-nickel secondary battery.
The invention is to solve the problemsThe technical scheme is that the preparation method of the zinc cathode material of the zinc-nickel secondary battery is characterized by comprising the following steps: dissolving soluble zinc salt, soluble tin salt and soluble copper salt in deionized water, adding a precipitator for precipitation, then filtering, washing, drying, placing in a tubular furnace, heating to 700-1050 ℃ in inert atmosphere, keeping the temperature for 1-10 h, and cooling to room temperature along with the furnace to obtain a target product Zn-Ni secondary battery zinc cathode material containing Zn, sn and Cu x Cu y SnO 4 The crystal, wherein x + y =2,x > 0,y > 0, the zinc-nickel secondary battery zinc cathode material Zn x Cu y SnO 4 The crystal is used as a cathode active substance or an additive of the zinc-nickel secondary battery, can improve the power and the specific energy performance of the zinc-nickel secondary battery, prevent the zinc cathode of the zinc-nickel secondary battery from expanding, falling off and dendritic crystal growth, and further prolong the service life of the zinc-nickel secondary battery;
the soluble zinc salt is one or more of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate; the soluble tin salt is one or more of stannous chloride, stannous sulfate, stannic chloride or stannous nitrate; the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate or copper acetate; the precipitator is one or more of sodium hydroxide solution, ammonia water or oxalic acid solution.
Preferably, the inert atmosphere is one or more of a nitrogen atmosphere, an argon atmosphere or a hydrogen atmosphere.
Preferably, the preparation method of the zinc cathode material of the zinc-nickel secondary battery is characterized in that the zinc cathode material ZnCuSnO 4 The specific preparation steps of the crystal are as follows: zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1 4 Crystal, the zinc cathode material ZnCuSnO 4 The crystal can be used for zinc-nickel secondary electricityThe active material or additive of the cathode of the cell can effectively improve the cycling stability of the zinc-nickel secondary battery;
the zinc cathode material ZnCuSnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR binding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, spot welding the electrode lugs to form negative electrodes on the foamed nickel substrate, sandwiching a negative electrode between two positive plates of nickel hydroxide, isolating the positive and negative electrodes by a diaphragm, and activating by charging and discharging for 3 times, the capacity is 230mAh/g.
Preferably, the preparation method of the zinc cathode material of the zinc-nickel secondary battery is characterized in that the zinc cathode material Zn 1.5 Cu 0.5 SnO 4 The specific preparation steps of the crystal are as follows: zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1.5 1.5 Cu 0.5 SnO 4 Crystal of the zinc negative electrode material Zn 1.5 Cu 0.5 SnO 4 The crystal can be used as a negative electrode active substance or an additive of a zinc-nickel secondary battery, and can effectively improve the cycling stability of the zinc-nickel secondary battery;
the zinc cathode material Zn 1.5 Cu 0.5 SnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR binding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, the electrode lugs are spot-welded to form a negative electrode, a negative electrode is sandwiched between two positive plates of nickel hydroxide, the positive and negative electrodes are isolated by a diaphragm, and after 3 times of charging and discharging activation, the capacity is measured to be 300mAh/g.
Compared with the prior art, the invention has the following beneficial effects: the zinc cathode material Zn prepared by the invention 2 SnO 4 The crystal can be used as a cathode active substance or an additive of a zinc-nickel secondary battery, and can effectively improve zinc and nickelThe power and specific energy performance of the secondary battery can prevent the zinc cathode of the zinc-nickel secondary battery from expanding, falling off and dendritic crystal growth, prolong the service life of the zinc-nickel secondary battery and meet the requirements of commercial application and environmental protection.
Drawings
FIG. 1 shows ZnCuSnO prepared in example 1 4 The charge-discharge contrast curve of the negative electrode material and the conventional zinc negative electrode material is obtained;
FIG. 2 is a ZnCuSnO alloy prepared in example 2 4 The charge-discharge contrast curve of the negative electrode material and the conventional zinc negative electrode material is obtained;
FIG. 3 is a ZnCuSnO doped 4 The charge-discharge curve of the zinc negative electrode material.
Detailed Description
The present invention is described in further detail below with reference to examples, but it should not be understood that the scope of the subject matter of the present invention is limited to the examples below, and any technique realized based on the above contents of the present invention falls within the scope of the present invention.
Example 1
Zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1 4 Crystal, the zinc cathode material ZnCuSnO 4 The crystal can be used as a cathode active substance or an additive of a zinc-nickel secondary battery, and can effectively improve the cycling stability of the zinc-nickel secondary battery;
the zinc cathode material ZnCuSnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR binding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, the electrode lugs are spot-welded to form a negative electrode on the foamed nickel substrate, a negative electrode is sandwiched between two positive plates of nickel hydroxide, the positive electrode and the negative electrode are isolated by a diaphragm, and after 3 times of charging and discharging activation, the capacity is measured to be 230mAh/g.
Example 2
Zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1.5 1.5 Cu 0.5 SnO 4 Crystal of the zinc negative electrode material Zn 1.5 Cu 0.5 SnO 4 The crystal can be used as a negative electrode active substance or an additive of a zinc-nickel secondary battery, and can effectively improve the cycling stability of the zinc-nickel secondary battery;
the zinc cathode material Zn 1.5 Cu 0.5 SnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR binding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, spot welding the electrode lugs to form negative electrodes on the foamed nickel substrate, sandwiching a negative electrode between two positive plates of nickel hydroxide, isolating the positive and negative electrodes by a diaphragm, and activating by charging and discharging for 3 times, the capacity is 300mAh/g.
The invention has the characteristics of easy purchase and acquisition, low price and the like of the materials, prepares the zinc cathode material of the zinc-nickel secondary battery, solves or partially solves the problems of expansion, falling and dendritic crystal growth of the zinc cathode material of the current zinc-nickel secondary battery, improves the cycle stability of the zinc-nickel secondary battery, and prolongs the service life of the zinc-nickel secondary battery.
While there have been shown and described what are at present considered the fundamental principles of the invention, its essential features and advantages, the invention further resides in various changes and modifications which fall within the scope of the invention as claimed.
Claims (4)
1. A preparation method of a zinc cathode material of a zinc-nickel secondary battery is characterized by comprising the following specific steps: dissolving soluble zinc salt, soluble tin salt and soluble copper salt in deionized water according to a certain proportion, adding precipitant to make precipitationThen filtering, washing, drying, placing in a tube furnace, heating to 700-1050 ℃ in inert atmosphere, preserving heat for 1-10 h, and cooling to room temperature along with the furnace to obtain the target product Zn-Ni secondary battery zinc cathode material Zn containing Zn, sn and Cu x Cu y SnO 4 The crystal, wherein x + y =2,x > 0,y > 0, the zinc-nickel secondary battery zinc cathode material Zn x Cu y SnO 4 The crystal is used for the cathode active substance of the zinc-nickel secondary battery, can improve the power and specific energy performance of the zinc-nickel secondary battery, prevent the zinc cathode of the zinc-nickel secondary battery from expanding, falling off and dendritic crystal growth, and further prolong the service life of the zinc-nickel secondary battery;
the soluble zinc salt is one or more of zinc chloride, zinc sulfate, zinc nitrate or zinc acetate; the soluble tin salt is one or more of stannous chloride, stannous sulfate, stannic chloride or stannous nitrate; the soluble copper salt is one or more of copper chloride, copper sulfate, copper nitrate or copper acetate; the precipitator is one or more of sodium hydroxide solution, ammonia water or oxalic acid solution.
2. The method for preparing the zinc negative electrode material of the zinc-nickel secondary battery according to claim 1, which is characterized in that: the inert atmosphere is one or more of nitrogen or argon.
3. The method for preparing the zinc cathode material of the zinc-nickel secondary battery according to claim 1, wherein the zinc cathode material is ZnCuSnO 4 The specific preparation steps of the crystal are as follows: zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1 4 Crystal, the zinc cathode material ZnCuSnO 4 The crystal can be used as a cathode active material of a zinc-nickel secondary battery, and can effectively improve the cycle stability of the zinc-nickel secondary battery;
the zinc cathode material ZnCuSnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR binding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, the electrode lugs are spot-welded to form a negative electrode on the foamed nickel substrate, a negative electrode is sandwiched between two positive plates of nickel hydroxide, the positive electrode and the negative electrode are isolated by a diaphragm, and after 3 times of charging and discharging activation, the capacity is measured to be 230mAh/g.
4. The method for preparing the zinc negative electrode material of the zinc-nickel secondary battery according to claim 1, wherein the zinc negative electrode material Zn 1.5 Cu 0.5 SnO 4 The specific preparation steps of the crystal are as follows: zinc chloride, tin tetrachloride and copper chloride are mixed according to the element molar ratio Zn: sn: dissolving Cu =1.5 1.5 Cu 0.5 SnO 4 Crystal of the zinc negative electrode material Zn 1.5 Cu 0.5 SnO 4 The crystal can be used as a cathode active material of a zinc-nickel secondary battery, and can effectively improve the cycling stability of the zinc-nickel secondary battery;
the zinc cathode material Zn 1.5 Cu 0.5 SnO 4 5wt% of conductive graphite is added into the crystal, and paste with 10000cP viscosity is prepared by HPMC and SBR bonding agent and coated on the crystal with the density of 320g/m 2 After drying and rolling, the electrode lugs are spot-welded to form a negative electrode, a negative electrode is sandwiched between two positive plates of nickel hydroxide, the positive and negative electrodes are isolated by a diaphragm, and after 3 times of charging and discharging activation, the capacity is measured to be 300mAh/g.
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