CN107706367B - Alkaline secondary cell negative electrode material [CuxZnyNizFe2O4] and using the negative electrode material battery - Google Patents

Alkaline secondary cell negative electrode material [CuxZnyNizFe2O4] and using the negative electrode material battery Download PDF

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CN107706367B
CN107706367B CN201710782777.1A CN201710782777A CN107706367B CN 107706367 B CN107706367 B CN 107706367B CN 201710782777 A CN201710782777 A CN 201710782777A CN 107706367 B CN107706367 B CN 107706367B
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negative electrode
secondary cell
copper
nickel
electrode material
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CN107706367A (en
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上官恩波
王芹
李晶
付淑倩
常照荣
李全民
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Henan Normal University
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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
    • H01M4/362—Composites
    • 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
    • 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
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/521—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of iron for aqueous cells
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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

Abstract

The invention discloses a kind of alkaline secondary cell negative electrode material C uxZnyNizFe2O4And the battery using the negative electrode material, belong to secondary battery cathode material technical field.Technical solution of the present invention main points are as follows: alkaline secondary cell negative electrode material, by spinel structure acid ferric complex salt [CuxZnyNizFe2O4] or spinel structure acid ferric complex salt [CuxZnyNizFe2O4] constituted with the composite material that carbon material forms, wherein 0,0.5 > z > 0 of 0.95 >=x >=0.5,0.5 > y >, x+y+z=1.The invention also discloses the preparation method of the alkaline secondary cell negative electrode material and its applications in alkaline secondary cell negative electrode plate.Negative electrode material 0.2C electric discharge gram volume produced by the present invention reaches 530mAh/g, and 5C puts a gram volume and reaches 480mAh/g, has the advantages that low in cost, high rate capability is good and has extended cycle life using alkaline secondary cell prepared by the negative electrode material.

Description

Alkaline secondary cell negative electrode material [CuxZnyNizFe2O4] and using the negative electrode material Battery
Technical field
The invention belongs to alkaline secondary cell negative electrode field of material technology, and in particular to a kind of alkaline secondary cell negative electrode material Material and preparation method thereof and the battery for using the negative electrode material.
Background technique
Alkaline secondary cell (for example Cd-Ni secondary battery, ni-mh rechargeable battery, zinc-nickel secondary batteries, iron nickel secondary batteries) Relative to lithium ion battery, due to being widely used in various storages by people with safety is good and the particular advantages such as cost performance height It can device.The problem of environmental pollution as existing for cadmium cathode, application of the Cd-Ni secondary battery in commercial market have been limited at present System.Since hydrogen storage alloy negative active material price is higher, the development of Ni-H cell, which receives, greatly to be limited.The secondary electricity of zinc-nickel Pond market is currently in development.But the zinc load used due to zinc-nickel secondary batteries the problems such as there are deformation and dendrite, such The cycle life of type battery is poor, it would be highly desirable to improve.In recent years, the development of iron nickel secondary batteries is widely noticed.However, with four oxidations Three-iron is iron cathode the problem of always existing passivation and liberation of hydrogen of main active substances, cause its high rate performance poor (< 2C) and Active material utilization efficiency is low (practical gram volume is only capable of reaching 200-300mAh/g), seriously constrains the hair of the type battery Exhibition.Alkaline secondary cell it is usually used be technique relative maturity nickel anode, the relevant technologies progress of cathode is clearly to restrict Its key factor developed.Currently, the exploitation of novel anode material is to promote the important means of alkaline secondary cell development, Receive the extensive concern of researcher.
Summary of the invention
The technical problem to be solved by the present invention is to provide a kind of cheap, good rate capability and excellent new of cycle performance Type alkaline secondary cell negative electrode material and preparation method thereof and the battery for using the negative electrode material.
The present invention adopts the following technical scheme that solve above-mentioned technical problem, alkaline secondary cell negative electrode material, feature It is by spinel structure ferrite [CuxZnyNizFe2O4] or spinel structure ferrite [CuxZnyNizFe2O4] and carbon The composite material of material composition is constituted, wherein 0,0.5 > z > 0, x+y+z=1 of 0.95 >=x >=0.5,0.5 > y >.
It further limits, the spinel structure ferrite [CuxZnyNizFe2O4] with carbon material composition composite material Middle carbon material is crystalline flake graphite, carbon nanotube, graphene, acetylene black, Ketjen black or carbon fiber, the matter of carbon material in composite material Amount percentage composition is 0.1%-20%.
The preparation method of alkaline secondary cell negative electrode material of the present invention, it is characterised in that the spinel structure Ferrite [CuxZnyNizFe2O4] negative electrode material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble nickel salt and soluble zinc salt are add to deionized water preparation The copper and iron nickel zinc composite compaction technique for being 0.5-7mol/L at molar concentration；
(2) alkaline hydrated oxide is dissolved in the alkaline solution for being configured to that molar concentration is 1-8mol/L in deionized water；
(3) alkaline solution is added in copper and iron nickel zinc composite compaction technique in 15-80 DEG C, is stirred continuously until that reaction is completed The pH value of mixed liquor is 7-14 afterwards；
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 1-48h, after being cooled to room temperature, is passed through It filters, wash, be dried to obtain brown powder；
(5) under inert nitrogen gas or argon atmosphere or air atmosphere, by brown powder in 300-800 DEG C of heat treatment 1- For 24 hours, it grinds, target product spinel structure ferrite [Cu is obtained after sievingxZnyNizFe2O4] negative electrode material.
The preparation method of alkaline secondary cell negative electrode material of the present invention, it is characterised in that the spinel structure Ferrite [CuxZnyNizFe2O4] with carbon material composition composite negative pole material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble nickel salt and soluble zinc salt are add to deionized water preparation The copper and iron nickel zinc composite compaction technique for being 0.5-7mol/L at molar concentration, then carbon material is evenly spread into copper and iron nickel zinc complex salt The copper and iron nickel zinc composite compaction technique containing carbon material is obtained in solution；
(2) alkaline hydrated oxide is dissolved in the alkaline solution for being configured to that molar concentration is 1-8mol/L in deionized water；
(3) alkaline solution is added in the copper and iron nickel zinc composite compaction technique containing carbon material in 15-80 DEG C, it is lasting to stir The pH of mixed liquor is 7-14 after until the reaction is complete；
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 1-48h, after being cooled to room temperature, is passed through It filters, wash, be dried to obtain black powder；
(5) under inert nitrogen gas or argon atmosphere or air atmosphere, by black powder in 300-800 DEG C of heat treatment 1- For 24 hours, it grinds, target product spinel structure ferrite [Cu is obtained after sievingxZnyNizFe2O4] compound with carbon material composition Negative electrode material.
It further limits, the soluble copper salt is copper nitrate, copper sulphate, copper acetate or copper chloride, the soluble iron Salt is ferric nitrate, ferric sulfate, ferric acetate or iron chloride, and the soluble zinc salt is zinc nitrate, zinc sulfate, zinc acetate or chlorination Zinc, the soluble nickel salt are nickel nitrate, nickel sulfate, nickel acetate or nickel chloride, and the alkaline hydrated oxide is sodium hydroxide, hydrogen Potassium oxide or lithium hydroxide.
Alkaline secondary cell negative electrode plate of the present invention, it is characterised in that: the alkaline secondary cell negative electrode plate be by What above-mentioned alkaline secondary cell negative electrode material was prepared.
It further limits, the alkaline secondary cell negative electrode plate includes on cathode carrier and cathode carrier or interior active matter Matter, the active material are prepared by the raw material that following weight percent matches: spinel structure ferrite [CuxZnyNizFe2O4] negative electrode material 50%-90%, additive 5%-40%, conductive agent 1%-20% and adhesive solution 0.5%-5% or spinel structure ferrite [CuxZnyNizFe2O4] with carbon material composition composite negative pole material 55%- 90%, additive 5%-40% and adhesive solution 0.5%-5%.
The preparation method of alkaline secondary cell negative electrode plate of the present invention, it is characterised in that specific steps are as follows: first will Spinel structure ferrite [the Cu that weight percent proportion is 50%-90%xZnyNizFe2O4] negative electrode material, weight percent match Than for 5%-40% additive and weight percent proportion be 1%-20% conductive agent be uniformly mixed or match weight percent For the spinel structure ferrite [Cu of 55%-90%xZnyNizFe2O4] composite negative pole material and again with carbon material composition It measures the additive that per distribution ratio is 5%-40% to be uniformly mixed, is then added to the binder that weight percent proportion is 0.5%-5% It in aqueous solution, stirs evenly and active material slurry is made, then active material slurry obtained is coated on cathode matrix, warp Cross drying, tabletting, punching, soldering polar ear, obtained alkaline secondary cell negative electrode plate.
Further limit, the additive be nickel sulfate, nickel sulfide, vulcanize sub- cobalt, bismuth oxide, bismuth sulfide, ferrous sulfide, Carbonyl iron dust, ferroso-ferric oxide, ferriferrous sulfide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide At least two in titanium or staple fiber；The conductive agent be superconduction graphite, crystalline flake graphite, Ketjen black, superconduction carbon black, acetylene black, One of carbon nanotube, graphene, oxidation titanous, nickel powder, cobalt powder, copper powder or glass putty are a variety of；The binder is poly- four One of vinyl fluoride, sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of；It is described Cathode matrix is perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, foam copper, foaming iron or copper mesh.
Alkaline secondary cell of the present invention, including battery case and it is sealed in the intracorporal polar plate group of battery case and electrolysis Liquid, wherein polar plate group includes positive plate, negative plate and diaphragm, it is characterised in that: the negative plate uses above-mentioned alkali secondary Cell negative plate.
Compared with the prior art, the invention has the following beneficial effects: spinel structure ferrite [CuxZnyNizFe2O4] And its carbon composite passes through the synergistic effect and composite optimization of multiple beneficial metal ion, greatly improves its charge and discharge cycles Structural stability in the process；The doping of different metal ions has regulated and controled high rate performance and the liberation of hydrogen behavior of the new material, pole The generation of big reduction evolving hydrogen reaction, improves charge efficiency, improves the volumetric properties of material.Zinc ion doped with being conducive to Improve the cyclical stability of material.Nickel ion doped be conducive to inhibit iron electrode passivation.Copper ion, which has, utilizes improvement material High rate performance.The compound electric conductivity that can it significantly further improve electrode with carbon material simultaneously reduces activation polarization, Improve the high rate performance and cycle performance of battery.By the synergistic effect of these metallic elements and carbon, electrode formulation it is excellent Change, the 0.2C electric discharge gram volume of the new material can be made to reach 530mAh/g, 5C puts a gram volume and reaches 480mAh/g, 1C Capacity retention ratio reaches 92% after circulation 200 times.Alkaline secondary cell using novel anode material preparation has specific energy High, good rate capability and the advantages of have extended cycle life.
Detailed description of the invention
Fig. 1 is the XRD diagram of alkaline secondary cell negative electrode material made from embodiment and comparative example；
Fig. 2 is [Cu made from embodiment0.6Zn0.3Ni0.1Fe2O4] negative electrode material SEM figure；
Fig. 3 is [Cu made from embodiment0.6Zn0.3Ni0.1Fe2O4The TEM of]/graphene composite negative pole schemes.
Specific embodiment
Above content of the invention is described in further details by the following examples, but this should not be interpreted as to this The range for inventing above-mentioned theme is only limitted to embodiment below, and all technologies realized based on above content of the present invention belong to this hair Bright range.
Embodiment 1
[Cu0.8Zn0.1Ni0.1Fe2O4] negative electrode material preparation:
Copper chloride, zinc sulfate, nickel chloride and ferric sulfate are added in molar ratio for Cu/Zn/Ni/Fe=0.8/0.1/0.1/2 Enter to be configured to the copper and iron nickel zinc composite compaction technique that total mol concentration is 3mol/L into deionized water；By potassium hydroxide be dissolved in from The potassium hydroxide solution that molar concentration is 3mol/L is configured in sub- water；Potassium hydroxide solution is added to copper and iron nickel zinc in 30 DEG C The pH that mixed liquor is adjusted in composite compaction technique is 13, persistently stirs 40min；Mixed liquor is transferred in hydrothermal reaction kettle in 130 DEG C Hydro-thermal reaction 5h after being cooled to room temperature, is filtered, washed, obtains brown powder in 80 DEG C of dry 5h；In a nitrogen atmosphere, will Brown powder obtains target product [Cu in 700 DEG C of heat treatment 1h, grinding after sieving0.8Zn0.1Ni0.1Fe2O4] negative electrode material.
[Cu0.8Zn0.1Ni0.1Fe2O4] negative electrode material application:
By [the Cu of synthesis0.8Zn0.1Ni0.1Fe2O4] negative electrode material 82g, bismuth oxide 4g, ferrous sulfide 6g, crystalline flake graphite 5g, The PTFE aqueous solution 0.2g that the HPMC solution 1.4g and mass concentration that mass concentration is 2.5% are 60% is uniformly mixed, and is made negative Pole slurry is applied on Foamed Nickel two sides by coating-spreading mould, by drying, roll-in, cuts negative plate is made.It will sintering anode Folder is fitted into special simulated battery shell across alkaline battery separator between plate and negative plate, and implantation quality concentration is 30% The LiOH electrolyte that KOH and mass concentration are 2%, is assembled into the alkaline secondary cell of semitight.
Embodiment 2
[Cu0.5Zn0.3Ni0.2Fe2O4] negative electrode material preparation:
It is in molar ratio that Cu/Zn/Ni/Fe=0.5/0.3/0.2/2 is added by copper nitrate, zinc sulfate, nickel sulfate, iron chloride The copper and iron nickel zinc composite compaction technique that total mol concentration is 4mol/L is configured into deionized water；Sodium hydroxide is dissolved in deionization The sodium hydroxide solution that molar concentration is 4mol/L is configured in water；Sodium hydroxide solution copper and iron nickel zinc is added in 20 DEG C to answer Closing and adjusting the pH of mixed liquor in salting liquid is 11, persistently stirs 30min；Mixed liquor is transferred in hydrothermal reaction kettle in 150 DEG C of water Thermal response 20h after being cooled to room temperature, is filtered, washed, obtains brown powder in 80 DEG C of dry 5h；It in a nitrogen atmosphere, will be brown Color powder obtains target product [Cu in 600 DEG C of heat treatment 4h, grinding after sieving0.5Zn0.3Ni0.2Fe2O4] negative electrode material.
[Cu0.5Zn0.3Ni0.2Fe2O4] negative electrode material application:
By [the Cu of synthesis0.5Zn0.3Ni0.2Fe2O4] negative electrode material 83g, ceria 2g, yttrium oxide 2g, ferrous sulfide 5g, The PTFE aqueous solution 0.2g mixing that the poly-vinyl alcohol solution 1.5g and mass concentration that acetylene black 5g, mass concentration are 4% are 60% Uniformly, negative electrode slurry is made, is applied on Foamed Nickel two sides by coating-spreading mould, by drying, roll-in, cuts cathode is made Plate.It folder will be fitted into special simulated battery shell, implantation quality is dense across alkaline battery separator between sintering positive plate and negative plate The LiOH electrolyte that the KOH and mass concentration that degree is 30% are 2%, is assembled into the alkaline secondary cell of semitight.
Embodiment 3
[Cu0.6Zn0.3Ni0.1Fe2O4] negative electrode material preparation:
Copper sulphate, zinc sulfate, nickel sulfate and ferric nitrate are added in molar ratio for Cu/Zn/Ni/Fe=0.6/0.3/0.1/2 Enter to be configured to the copper and iron nickel zinc composite compaction technique that total mol concentration is 2mol/L in deionized water；Potassium hydroxide is dissolved in deionization The potassium hydroxide solution that molar concentration is 1mol/L is configured in water；Potassium hydroxide solution copper and iron nickel zinc is added in 30 DEG C to answer Closing and adjusting the pH of mixed liquor in salting liquid is 12, persistently stirs 40min；Mixed liquor is transferred in hydrothermal reaction kettle in 170 DEG C of water Thermal response 1h after being cooled to room temperature, is filtered, washed, obtains brown powder in 80 DEG C of dry 5h；It in air atmosphere, will be brown Color powder obtains target product [Cu in 500 DEG C of heat treatment 10h, grinding after sieving0.6Zn0.3Ni0.1Fe2O4] negative electrode material.
[Cu0.6Zn0.3Ni0.1Fe2O4] negative electrode material application:
By [the Cu of synthesis0.6Zn0.3Ni0.1Fe2O4] negative electrode material 68g, erbium oxide 2g, ferroso-ferric oxide 10g, ferrous sulfide The PTFE water that the HPMC solution 1.4g and mass concentration that 10g, superconduction carbon black 5g, nickel powder 5g, mass concentration are 2.5% are 60% Solution 0.2g is uniformly mixed, and negative electrode slurry is made, is applied on foam copper two sides by coating-spreading mould, by drying, roll-in, sanction Cut into negative plate.It folder will be fitted into special simulated battery shell across alkaline battery separator between sintering positive plate and negative plate, The LiOH electrolyte that the KOH and mass concentration that implantation quality concentration is 30% are 2% is assembled into the alkali secondary electricity of semitight Pond.
Embodiment 4
[Cu0.6Zn0.3Ni0.1Fe2O4The preparation of]/RGO composite negative pole material:
Copper chloride, zinc sulfate, nickel chloride and ferric sulfate are added in molar ratio for Cu/Zn/Ni/Fe=0.6/0.3/0.1/2 Enter to be configured to the copper and iron nickel zinc composite compaction technique that total mol concentration is 3mol/L into deionized water, by a certain amount of graphite oxide Alkene is distributed to the copper and iron nickel zinc composite compaction technique obtained in copper and iron nickel zinc composite compaction technique containing carbon material, controls final sample Carbon content is 10%；Potassium hydroxide is dissolved in the potassium hydroxide solution for being configured to that molar concentration is 3mol/L in deionized water；In The pH value that potassium hydroxide solution is added to adjusting mixed liquor in the copper and iron zinc composite compaction technique containing carbon material is 13 by 30 DEG C, is held Continuous stirring 40min；Mixed liquor is transferred in hydrothermal reaction kettle in 130 DEG C of hydro-thermal reaction 5h, after being cooled to room temperature, filtered, washed It washs, obtain black powder in 80 DEG C of dry 5h；In a nitrogen atmosphere, black powder is ground in 600 DEG C of heat treatment 1h, sieving After obtain target product [Cu0.6Zn0.3Ni0.1Fe2O4]/RGO composite negative pole material.
[Cu0.6Zn0.3Ni0.1Fe2O4The application of]/RGO negative electrode material:
By [the Cu of synthesis0.6Zn0.3Ni0.1Fe2O4]/RGO composite negative pole material 62g, ferrous sulfide 20g, ceria 5g The poly-vinyl alcohol solution 1.5g for being 4% with mass concentration is uniformly mixed, and negative electrode slurry is made, is applied to foaming by coating-spreading mould On nickel two sides, by drying, roll-in, cuts negative plate is made.It will press from both sides between sintering positive plate and negative plate across alkaline battery Diaphragm is fitted into special simulated battery shell, the LiOH electrolysis that the KOH and mass concentration that implantation quality concentration is 30% are 2% Liquid is assembled into the alkaline secondary cell of semitight.
Comparative example 1
[CuFe2O4] negative electrode material preparation:
It is in molar ratio to be configured to total mol concentration in Cu/Fe=1/2 addition deionized water to be by copper chloride and ferric sulfate The copper and iron composite compaction technique of 1mol/L；Potassium hydroxide is dissolved in the hydrogen-oxygen for being configured to that molar concentration is 1mol/L in deionized water Change potassium solution；It is 14 that potassium hydroxide solution, which is added to the pH of adjusting mixed liquor in copper and iron composite compaction technique, in 20 DEG C, is persistently stirred Mix 30min；Mixed liquor is transferred in hydrothermal reaction kettle in 150 DEG C of hydro-thermal reaction 2h, after being cooled to room temperature, be filtered, washed, Brown powder is obtained in 80 DEG C of dry 5h；In a nitrogen atmosphere, by brown powder in 500 DEG C of heat treatment 2h, grinding obtains after sieving To target product [CuFe2O4] negative electrode material.
[CuFe2O4] negative electrode material application:
By [the CuFe of synthesis2O4] negative electrode material 82g, bismuth sulfide 5g, ferrous sulfide 5g, superconduction carbon black 5g, mass concentration be The PTFE aqueous solution 0.2g that 2.5% HPMC solution 1.4g and mass concentration is 60% is uniformly mixed, and negative electrode slurry is made, passes through Coating-spreading mould is applied on Foamed Nickel two sides, by drying, roll-in, cuts negative plate is made.It will sintering positive plate and negative plate Between folder across alkaline battery separator, be fitted into special simulated battery shell, implantation quality concentration be 30% KOH and quality it is dense The LiOH electrolyte that degree is 2%, is assembled into the alkaline secondary cell of semitight.
Comparative example 2
[Cu0.9Zn0.1Fe2O4] negative electrode material preparation:
It is in molar ratio to match in Cu/Zn/Fe=0.9/0.1/2 addition deionized water by copper sulphate, zinc chloride and iron chloride The copper and iron zinc composite compaction technique that total mol concentration is 2mol/L is made；Sodium hydroxide is dissolved in deionized water be configured to it is mole dense Degree is the sodium hydroxide solution of 1mol/L；Sodium hydroxide solution is added to adjust in copper and iron zinc composite compaction technique in 20 DEG C and is mixed The pH for closing liquid is 12, persistently stirs 30min；Mixed liquor is transferred in hydrothermal reaction kettle in 140 DEG C of hydro-thermal reaction 4h, is cooled to It after room temperature, is filtered, washed, obtains brown powder in 80 DEG C of dry 5h；In a nitrogen atmosphere, by brown powder in 500 DEG C of heat 10h is handled, grinding obtains target product [Cu after sieving0.9Zn0.1Fe2O4] negative electrode material.
[Cu0.9Zn0.1Fe2O4] negative electrode material application:
By [the Cu of synthesis0.9Zn0.1Fe2O4] negative electrode material 82g, bismuth sulfide 5g, ferriferrous sulfide 5g, superconduction carbon black 5g, matter Measure concentration be 2.5% CMC solution 1g, mass concentration be 4% poly-vinyl alcohol solution 0.5g and mass concentration be 60% PTFE aqueous solution 0.3g is uniformly mixed, and negative electrode slurry is made, is applied on steel band two sides by coating-spreading mould, by drying, roller It presses, cut negative plate is made.Special simulated battery will be packed into across alkaline battery separator by folder between sintering positive plate and negative plate In shell, the LiOH electrolyte that the KOH and mass concentration that implantation quality concentration is 30% are 2% is assembled into the alkalinity two of semitight Primary cell.
Comparative example 3
[Cu0.9Ni0.1Fe2O4] negative electrode material preparation:
It is in molar ratio that deionized water is added in Cu/Ni/Fe=0.9/0.1/2 by copper chloride, sulphation nickel and sulfuric acid copper and iron In be configured to total mol concentration be 1mol/L copper and iron nickel composite compaction technique；Sodium hydroxide is dissolved in and is configured to rub in deionized water The sodium hydroxide solution that your concentration is 2mol/L；Sodium hydroxide solution is added in copper and iron nickel composite compaction technique in 50 DEG C and is adjusted The pH for saving mixed liquor is 14, persistently stirs 20min；Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 8h, it is cold But it to after room temperature, is filtered, washed, obtains brown powder in 80 DEG C of dry 5h；In a nitrogen atmosphere, by brown powder in 600 DEG C heat treatment 1h, grinding, target product [Cu is obtained after sieving0.9Ni0.1Fe2O4] negative electrode material.
[Cu0.9Ni0.1Fe2O4] negative electrode material application:
By [the Cu of synthesis0.9Ni0.1Fe2O4] negative electrode material 82g, zinc oxide 5g, bismuth sulfide 5g, carbon nanotube 5g, quality be dense Spending the HPMC solution 1.2g for 2.5%, the poly-vinyl alcohol solution 0.3g that mass concentration is 4% and mass concentration is 60% PTFE aqueous solution 0.2g be uniformly mixed, negative electrode slurry is made, is applied on Foamed Nickel two sides by coating-spreading mould, by drying, Roll-in cuts negative plate is made.Special simulation electricity will be packed into across alkaline battery separator by folder between sintering positive plate and negative plate In the shell of pond, the LiOH electrolyte that the KOH and mass concentration that implantation quality concentration is 30% are 2% is assembled into the alkalinity of semitight Secondary cell.
Sample segment characterization:
The XRD diffraction test results of portioned product are as shown in Figure 1, by Fig. 1 and coppe ferrite in above-described embodiment and comparative example Standard diffraction peak compare, it can be found that its data is very identical with base peak, illustrate that other elements (zinc, nickel) mix well Ferrite lattice, has obtained the higher composite mixed ferrous acid product salt of purity.
[Cu0.6Zn0.3Ni0.1Fe2O4] test results are shown in figure 2 by the SEM of negative electrode material.By Fig. 2 it can be seen that, above-mentioned reality Apply [Cu obtained in example0.6Zn0.3Ni0.1Fe2O4] negative electrode material presentation spherical particle pattern, primary particle is nanoscale Grain. [Cu0.6Zn0.3Ni0.1Fe2O4Test results are shown in figure 3 by the TEM of]/RGO negative electrode material.By Fig. 2 it can be seen that, above-mentioned reality Apply [Cu obtained in example0.6Zn0.3Ni0.1Fe2O4] negative electrode material presentation spherical particle pattern, it is supported on graphene.Wherein, Primary particle is nano-scale particle, and diameter is about 30-50nm.
Battery performance test:
Volume test: by the simulated battery prepared using specific embodiment 1-4 and comparative example 1-3 after 0.2C is activated, 0.2C charging 6h, battery shelves 30min later, is then discharged to voltage respectively with 0.2C and 5C as 1.0V and 0.8V, measurement is negative The volumetric properties of pole material.Cycle performance of battery test: battery made from specific embodiment 1-4 and comparative example 1-3 is existed respectively 1C charge-discharge test is carried out under 25 DEG C of environment temperatures, is recycled 200 times.
Battery electrical property test result is listed in Table 1.
1 battery charging/discharging performance testing of table
It can be seen that from the above test result using negative electrode material prepared by the present invention gram volume with higher, excellent High rate performance and cyclical stability, be able to satisfy commercial cells, the especially requirement of high capacity high-power battery.These performances Improvement be mainly due to: 1) exploitation of the capacity of sample is played to pass in the optimization of synthetic method, especially including high temperature processes Important role；2) modification and regulating and controlling effect of the doping of beneficial metal ion zinc and nickel to negative electrode material structural lattice, greatly Ground improves the volumetric properties and cycle performance of material, especially high rate capability；3) the composite mixed of carbon material is conducive to change The electric conductivity of kind material promotes capacity exploitation and high-current leading to use；4) research also found, the optimization of electrode formulation is to influence ferrous acid One of the key factor of salt electrode performance.Reasonable electrode formulation optimization is to improve the important means of the material overall performance.
Embodiment above describes basic principles and main features of the invention and advantages.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments, and the above embodiments and description only describe originals of the invention Reason, under the range for not departing from the principle of the invention, various changes and improvements may be made to the invention, these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (7)

1. alkaline secondary cell negative electrode material is preparing the application in alkaline secondary cell negative electrode plate, it is characterised in that: the alkali Property secondary battery cathode material is by spinel structure ferrite [CuxZnyNizFe2O4] or spinel structure ferrite [CuxZnyNizFe2O4] constituted with the composite material that carbon material forms, wherein 0,0.5 > z > of 0.95 >=x >=0.5,0.5 > y > 0, x+y+z=1；Alkaline secondary cell negative electrode plate includes the active material on cathode carrier and cathode carrier or interior active material It is prepared by the raw material that following weight percent matches: spinel structure ferrite [CuxZnyNizFe2O4] negative electrode material 50%- 90%, additive 5%-40%, conductive agent 1%-20% and adhesive solution 0.5%-5% or spinel structure ferrite [CuxZnyNizFe2O4] with carbon material composition composite negative pole material 55%-90%, additive 5%-40% and adhesive solution 0.5%-5%；The additive is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, bismuth oxide, bismuth sulfide, ferrous sulfide, carbonyl iron dust, four In Fe 3 O, ferriferrous sulfide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide or staple fiber At least two；The conductive agent is superconduction graphite, crystalline flake graphite, acetylene black, Ketjen black, superconduction carbon black, carbon nanotube, graphite One of alkene, oxidation titanous, nickel powder, cobalt powder, copper powder or glass putty are a variety of；The binder is polytetrafluoroethylene (PTFE), carboxymethyl One of sodium cellulosate, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of；The cathode matrix is perforation Steel band, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, foam copper, foaming iron or copper mesh.
2. alkaline secondary cell negative electrode material according to claim 1 is preparing answering in alkaline secondary cell negative electrode plate With, it is characterised in that: the spinel structure ferrite [CuxZnyNizFe2O4] with carbon material composition composite material in carbon Material is crystalline flake graphite, carbon nanotube, graphene oxide, acetylene black, Ketjen black or carbon fiber, the matter of carbon material in composite material Amount percentage composition is 0.1%-20%.
3. alkaline secondary cell negative electrode material according to claim 1 is preparing answering in alkaline secondary cell negative electrode plate With, it is characterised in that the spinel structure ferrite [CuxZnyNizFe2O4] negative electrode material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble nickel salt and soluble zinc salt are add to deionized water and are configured to rub The copper and iron nickel zinc composite compaction technique that your concentration is 0.5-7mol/L；
(2) alkaline hydrated oxide is dissolved in the alkaline solution for being configured to that molar concentration is 1-8mol/L in deionized water；
(3) alkaline solution is added in copper and iron nickel zinc composite compaction technique in 15-80 DEG C, is stirred continuously until and mixes after the reaction was completed The pH value for closing liquid is 7-14；
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 1-48h, after being cooled to room temperature, filtered, It washs, be dried to obtain brown powder；
(5) under inert nitrogen gas or argon atmosphere or air atmosphere, by brown powder in 300-800 DEG C of heat treatment 1-24h, Grinding, obtains target product spinel structure ferrite [Cu after sievingxZnyNizFe2O4] negative electrode material.
4. alkaline secondary cell negative electrode material according to claim 1 is preparing answering in alkaline secondary cell negative electrode plate With, it is characterised in that the spinel structure ferrite [CuxZnyNizFe2O4] composite negative pole material with carbon material composition Specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble nickel salt and soluble zinc salt are add to deionized water and are configured to rub You are the copper and iron nickel zinc composite compaction technique of 0.5-7mol/L at concentration, then carbon material is evenly spread to copper and iron nickel zinc composite compaction technique In obtain the copper and iron nickel zinc composite compaction technique containing carbon material；
(2) alkaline hydrated oxide is dissolved in the alkaline solution for being configured to that molar concentration is 1-8mol/L in deionized water；
(3) alkaline solution is added in the copper and iron nickel zinc composite compaction technique containing carbon material, is stirred continuously until in 15-80 DEG C The pH of mixed liquor is 7-14 after the reaction was completed；
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 1-48h, after being cooled to room temperature, filtered, It washs, be dried to obtain black powder；
(5) under inert nitrogen gas or argon atmosphere or air atmosphere, by black powder in 300-800 DEG C of heat treatment 1-24h, Grinding, obtains target product spinel structure ferrite [Cu after sievingxZnyNizFe2O4] with carbon material composition composite negative pole Material.
5. alkaline secondary cell negative electrode material according to claim 3 or 4 is in preparing alkaline secondary cell negative electrode plate Using, it is characterised in that: the soluble copper salt is copper nitrate, copper sulphate, copper acetate or copper chloride, and the soluble ferric iron salt is Ferric nitrate, ferric sulfate, ferric acetate or iron chloride, the soluble zinc salt are zinc nitrate, zinc sulfate, zinc acetate or zinc chloride, institute Stating soluble nickel salt is nickel nitrate, nickel sulfate, nickel acetate or nickel chloride, and the alkaline hydrated oxide is sodium hydroxide, hydroxide Potassium or lithium hydroxide.
6. alkaline secondary cell negative electrode material according to claim 1 is preparing answering in alkaline secondary cell negative electrode plate With, it is characterised in that the specific preparation step of alkaline secondary cell negative electrode plate are as follows: first match weight percent for 50%-90%'s Spinel structure ferrite [CuxZnyNizFe2O4] negative electrode material, weight percent proportion be 5%-40% additive and weight hundred The conductive agent that distribution ratio is 1%-20% is uniformly mixed or weight percent is matched the spinel structure ferrite for 55%-90% [CuxZnyNizFe2O4] mixed with the composite negative pole material of carbon material composition and weight percent proportion for the additive of 5%-40% Even, being then added to weight percent proportion is to stir evenly and active material slurry is made, so in the adhesive solution of 0.5%-5% Active material slurry obtained is coated on cathode matrix afterwards, by drying, tabletting, punching, soldering polar ear, obtained alkalinity two Primary cell negative plate；The additive is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, bismuth oxide, bismuth sulfide, ferrous sulfide, carbonyl iron Powder, ferroso-ferric oxide, ferriferrous sulfide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide or short At least two in fiber；The conductive agent is superconduction graphite, crystalline flake graphite, acetylene black, Ketjen black, superconduction carbon black, carbon nanometer One of pipe, graphene, oxidation titanous, nickel powder, cobalt powder, copper powder or glass putty are a variety of；The binder be polytetrafluoroethylene (PTFE), One of sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of；The cathode matrix For perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, foam copper, foaming iron or copper mesh.
7. a kind of alkaline secondary cell, including battery case and it is sealed in the intracorporal polar plate group of battery case and electrolyte, wherein pole Board group includes positive plate, negative plate and diaphragm, it is characterised in that: the negative plate is using alkalinity two described in claim 1 Primary cell negative plate.
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