CN107658441B - Alkaline secondary cell negative electrode material [CoxCuyZnzFe2O4] and using the negative electrode material battery - Google Patents
Alkaline secondary cell negative electrode material [CoxCuyZnzFe2O4] and using the negative electrode material battery Download PDFInfo
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- CN107658441B CN107658441B CN201710782775.2A CN201710782775A CN107658441B CN 107658441 B CN107658441 B CN 107658441B CN 201710782775 A CN201710782775 A CN 201710782775A CN 107658441 B CN107658441 B CN 107658441B
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- 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
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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
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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
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- 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
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- H—ELECTRICITY
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- 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
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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
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Abstract
The invention discloses a kind of alkaline secondary cell negative electrode material C oxCuyZnzFe2O4And 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 [CoxCuyZnzFe2O4] or spinel structure acid ferric complex salt [CoxCuyZnzFe2O4] constituted with the composite material of carbon material composition, wherein 10,0.7 > z > 0 of > x >=0.3,0.7 > y >, x+y+z=1.The invention further particularly 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 of the invention reaches 390mAh/g, and 5C electric discharge gram volume reaches 320mAh/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 novel anode material.
Description
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
Expect [CoxCuyZnzFe2O4] and preparation method thereof and using the negative electrode material battery.
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 low efficiency (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 [CoxCuyZnzFe2O4] and preparation method thereof and using the negative electrode material battery.
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 [CoxCuyZnzFe2O4] or spinel structure ferrite [CoxCuyZnzFe2O4] and carbon
The composite material of material composition is constituted, wherein 10,0.7 > z > 0, x+y+z=1 of > x >=0.3,0.7 > y >.
It further limits, the spinel structure ferrite [CoxCuyZnzFe2O4] 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 spinel structure ferrous acid
Salt [CoxCuyZnzFe2O4] negative electrode material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble cobalt and soluble zinc salt are add to deionized water preparation
The copper and iron cobalt 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 15-80 DEG C in copper and iron cobalt zinc composite compaction technique, is stirred continuously until that reaction is completed
The pH 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 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 [Co is obtained after sievingxCuyZnzFe2O4] negative electrode material.
The preparation method of alkaline secondary cell negative electrode material of the present invention, it is characterised in that spinel structure ferrous acid
Salt [CuxZnyNizFe2O4] with carbon material composition composite negative pole material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble cobalt and soluble zinc salt are add to deionized water preparation
The copper and iron cobalt zinc composite compaction technique for being 0.5-7mol/L at molar concentration, then carbon material is evenly spread into copper and iron cobalt zinc complex salt
The copper and iron cobalt 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 15-80 DEG C in the copper and iron cobalt zinc composite compaction technique containing carbon material, 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 cobalt are cobalt nitrate, cobaltous sulfate, cobalt acetate or cobalt 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 includes
There is above-mentioned alkaline secondary cell negative electrode material.
It further limits, the alkaline secondary cell negative electrode plate includes on cathode matrix and cathode matrix or interior active matter
Matter, the active material are prepared by the raw material that following weight percent matches: spinel structure ferrite
[CoxCuyZnzFe2O4] negative electrode material or spinel structure ferrite [CoxCuyZnzFe2O4] compound with carbon material composition
Negative electrode material 50%-93.5%, additive 5%-40%, conductive agent 1%-20% 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: will weigh first
Measure the spinel structure ferrite [Co that per distribution ratio is 50%-93.5%xCuyZnzFe2O4] negative electrode material or spinel-type knot
Structure ferrite [CoxCuyZnzFe2O4] with carbon material composition composite negative pole material, weight percent proportion be 5%-40% addition
The conductive agent that agent and weight percent proportion are 1%-20% is uniformly mixed, and being then added to weight percent is 0.5%-5%'s
It in adhesive solution, stirs evenly, active material slurry is made, active material slurry obtained is then coated in cathode base
On body, by 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 electrically conductive graphite, Ketjen black, conductive black, carbon nanotube, graphene,
Aoxidize one of titanous, nickel powder, cobalt powder, copper powder or glass putty or a variety of；The binder is polytetrafluoroethylene (PTFE), carboxymethyl cellulose
One of plain sodium, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of；The negative matrix body is perforation steel
Band, 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 [CoxCuyZnzFe2O4]
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.Copper ion, which has, utilizes the high rate performance for improving material.It simultaneously can be into the compound of carbon material
One step significantly improves the electric conductivity of electrode, reduces activation polarization, improves the high rate performance and cycle performance of battery.Pass through this
The synergistic effect of a little metallic elements and carbon, the optimization of electrode formulation can make the 0.2C electric discharge gram volume of the new material
Reach 390mAh/g, 5C electric discharge gram volume reaches 320mAh/g.Using the alkaline secondary cell tool of novel anode material preparation
The advantages of having high specific energy, good rate capability and having 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 [Co made from embodiment0.5Cu0.3Zn0.2Fe2O4] negative electrode material SEM figure.
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
[Co0.7Cu0.2Zn0.1Fe2O4] negative electrode material preparation:
Cobalt chloride, copper chloride, zinc sulfate and ferric sulfate are added in molar ratio for Co/Cu/Zn/Fe=0.7/0.2/0.1/2
Enter to be configured to the copper and iron cobalt zinc composite compaction technique that total mol concentration is 4mol/L into deionized water；By potassium hydroxide be dissolved in from
The potassium hydroxide solution that molar concentration is 1mol/L is configured in sub- water；Potassium hydroxide solution is added to copper and iron cobalt zinc in 30 DEG C
The pH that mixed liquor is adjusted in composite compaction technique is 14, persistently stirs 40min；Mixed liquor is transferred in hydrothermal reaction kettle in 110 DEG C
Hydro-thermal reaction 20h after being cooled to room temperature, is filtered, washed, obtains black powder in 80 DEG C of dry 5h；In air atmosphere, will
Black powder obtains target product [Co in 700 DEG C of heat treatment 1h, grinding after sieving0.7Cu0.2Zn0.1Fe2O4] negative electrode material.
[Co0.7Cu0.2Zn0.1Fe2O4] negative electrode material application:
By [the Co of synthesis0.7Cu0.2Zn0.1Fe2O4] negative electrode material 84g, ferrous sulfide 10g, bismuth oxide 4g, crystalline flake graphite
The PTFE aqueous solution 0.2g that the HPMC solution 1.4g and mass concentration that 5g, mass concentration are 2.5% are 60% is uniformly mixed, system
It at negative electrode slurry, is applied on Foamed Nickel two sides by coating-spreading mould, by drying, roll-in, cuts negative plate is made.It will sintering
Folder is fitted into special simulated battery shell across alkaline battery separator between positive plate and negative plate, and implantation quality concentration is 30%
KOH and mass concentration be 2% LiOH electrolyte, be assembled into the alkaline secondary cell of semitight.
Embodiment 2
[Co0.6Cu0.2Zn0.2Fe2O4] negative electrode material preparation:
Cobaltous sulfate, copper nitrate, zinc sulfate and ferric sulfate are added in molar ratio for Co/Cu/Zn/Fe=0.6/0.2/0.2/2
Enter to be configured to the cobalt copper and iron zinc composite compaction technique that total mol concentration is 2.5mol/L into deionized water；Potassium hydroxide is dissolved in
The potassium hydroxide solution that molar concentration is 6mol/L is configured in ionized water；Potassium hydroxide solution is added to cobalt copper and iron in 20 DEG C
The pH that mixed liquor is adjusted in zinc composite compaction technique is 14, persistently stirs 30min；Mixed liquor is transferred in hydrothermal reaction kettle in 160
DEG C hydro-thermal reaction for 24 hours, after being cooled to room temperature, is filtered, washed, obtains black powder in 80 DEG C of dry 5h；In air atmosphere,
By black powder in 700 DEG C of heat treatment 1h, grinding obtains target product [Co after sieving0.6Cu0.2Zn0.2Fe2O4] negative electrode material.
[Co0.6Cu0.2Zn0.2Fe2O4] negative electrode material application:
By [the Co of synthesis0.6Cu0.2Zn0.2Fe2O4] negative electrode material 83g, ceria 2g, zinc oxide 5g, ferrous sulfide 5g,
The PTFE aqueous solution 0.2g that the poly-vinyl alcohol solution 1.5g and mass concentration that acetylene black 5g, mass concentration are 4% are 60% is mixed
It closes uniformly, negative electrode slurry is made, is applied on Foamed Nickel two sides by coating-spreading mould, by drying, roll-in, cut 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
[Co0.5Cu0.3Zn0.2Fe2O4] negative electrode material preparation:
Cobaltous sulfate, copper sulphate, zinc sulfate and ferric nitrate are added in molar ratio for Co/Cu/Zn/Fe=0.5/0.3/0.2/2
Enter to be configured to the cobalt copper and iron 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 cobalt copper and iron zinc in 30 DEG C
The pH that mixed liquor is adjusted in composite compaction technique is 11, persistently stirs 40min；Mixed liquor is transferred in hydrothermal reaction kettle in 140 DEG C
Hydro-thermal reaction 1h after being cooled to room temperature, is filtered, washed, obtains black powder in 80 DEG C of dry 5h；In air atmosphere, will
Black powder obtains target product [Co in 500 DEG C of heat treatment 10h, grinding after sieving0.5Cu0.3Zn0.2Fe2O4] negative electrode material.
[Co0.5Cu0.3Zn0.2Fe2O4] negative electrode material application:
By [the Co of synthesis0.5Cu0.3Zn0.2Fe2O4] negative electrode material 68g, erbium oxide 2g, ferroso-ferric oxide 10g, ferrous sulfide
The PTFE aqueous solution 0.2g that the HPMC solution 1.4g and mass concentration that 10g, superconduction carbon black 5g, mass concentration are 2.5% are 60%
Be uniformly mixed, negative electrode slurry is made, is applied on foam copper two sides by coating-spreading mould, by drying, roll-in, cut be made it is negative
Pole plate.It folder will be fitted into special simulated battery shell, implantation quality across alkaline battery separator between sintering positive plate and negative plate
The LiOH electrolyte that the KOH and mass concentration that concentration is 30% are 2%, is assembled into the alkaline secondary cell of semitight.
Embodiment 4
[Co0.5Cu0.3Zn0.2Fe2O4The preparation of]/RGO composite negative pole material:
Cobalt nitrate, copper chloride, zinc sulfate and ferric sulfate are added in molar ratio for Co/Cu/Zn/Fe=0.5/0.3/0.2/2
Enter to be configured to the cobalt copper and iron 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 cobalt copper and iron zinc composite compaction technique obtained in cobalt copper and iron zinc composite compaction technique containing carbon material, controls final sample
Carbon content is 5%；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 that potassium hydroxide solution is added to adjusting mixed liquor in the cobalt 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；Under inert nitrogen gas atmosphere, by black powder in 600 DEG C of heat treatment 1h, grind
Mill, obtains target product [Co after sieving0.5Cu0.3Zn0.2Fe2O4]/RGO composite negative pole material.
[Co0.5Cu0.3Zn0.2Fe2O4The application of]/RGO composite negative pole material:
By [the Co of synthesis0.5Cu0.3Zn0.2Fe2O4]/RGO composite negative pole material 62g, ferrous sulfide 20g, ceria 5g,
Superconduction carbon black 5g, the poly-vinyl alcohol solution 1.5g that mass concentration is 4% are uniformly mixed, and negative electrode slurry is made, passes through coating-spreading mould
It is applied on Foamed Nickel two sides, by drying, roll-in, cuts negative plate is made.Will sintering positive plate and negative plate between folder every
Alkaline battery separator, be fitted into special simulated battery shell, the KOH and mass concentration that implantation quality concentration is 30% are 2%
LiOH electrolyte is assembled into the alkaline secondary cell of semitight.
Comparative example 1
[CoFe2O4] negative electrode material preparation:
It is in molar ratio that Co/Fe=1/2 is add to deionized water and is configured to total mol concentration by cobalt chloride and ferric sulfate
For the copper and iron composite compaction technique of 2mol/L；Potassium hydroxide is dissolved in the hydrogen for being configured to that molar concentration is 3mol/L in deionized water
Potassium oxide 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 continued
Stir 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；Under inert nitrogen gas atmosphere, by brown powder in 500 DEG C of heat treatment 2h, grind
Mill, obtains target product [CoFe after sieving2O4] negative electrode material.
[CoFe2O4] negative electrode material application:
By [the CoFe of synthesis2O4] negative electrode material 80g, bismuth sulfide 5g, superconduction carbon black 5g, the HPMC that mass concentration is 2.5%
The PTFE aqueous solution 0.2g that solution 1.4g and mass concentration are 60% is uniformly mixed, and negative electrode slurry is made, is applied by coating-spreading mould
On cloth to Foamed Nickel two sides, by drying, roll-in, cuts negative plate is made.Will sintering positive plate and negative plate between folder across
Alkaline battery separator is fitted into special simulated battery shell, and the KOH and mass concentration that implantation quality concentration is 30% are 2%
LiOH electrolyte is assembled into the alkaline secondary cell of semitight.
Comparative example 2
[Co0.7Cu0.3Fe2O4] negative electrode material preparation:
Cobaltous sulfate, copper chloride and iron chloride are add to deionized water in molar ratio for Co/Cu/Fe=0.7/0.3/2
It is configured to the copper and iron zinc composite compaction technique that total mol concentration is 5mol/L；Sodium hydroxide is dissolved in deionized water and is configured to mole
Concentration is the sodium hydroxide solution of 5mol/L；Sodium hydroxide solution is added in copper and iron zinc composite compaction technique in 20 DEG C and is adjusted
The pH of mixed liquor is 14, persistently stirs 30min；Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 6h, it is cooling
To room temperature, it is filtered, washed, obtains black powder in 80 DEG C of dry 5h；Under inert nitrogen gas atmosphere, by black powder
In 500 DEG C of heat treatment 10h, grinding obtains target product [Co after sieving0.7Cu0.3Fe2O4] negative electrode material.
[Co0.7Cu0.3Fe2O4] negative electrode material application:
By [the Co of synthesis0.7Cu0.3Fe2O4] negative electrode material 80g, bismuth sulfide 5g, ferriferrous sulfide 8g, 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
[Co0.7Zn0.3Fe2O4] negative electrode material preparation:
Cobaltous sulfate, zinc chloride and ferric sulfate are add to deionized water in molar ratio for Co/Zn/Fe=0.7/0.3/2
It is configured to the cobalt zinc ferrite composite compaction technique that total mol concentration is 1mol/L；Sodium hydroxide is dissolved in deionized water and is configured to mole
Concentration is the sodium hydroxide solution of 7mol/L；Sodium hydroxide solution is added in cobalt zinc ferrite composite compaction technique in 50 DEG C and is adjusted
The pH of mixed liquor is 12, persistently stirs 20min；Mixed liquor is transferred in hydrothermal reaction kettle in 140 DEG C of hydro-thermal reaction 8h, it is cooling
To room temperature, it is filtered, washed, obtains black powder in 80 DEG C of dry 5h；Under inert nitrogen gas atmosphere, by black powder
In 600 DEG C of heat treatment 1h, grinding obtains target product [Co after sieving0.7Zn0.3Fe2O4] negative electrode material.
[Co0.7Zn0.3Fe2O4] negative electrode material application:
By [the Co of synthesis0.7Zn0.3Fe2O4] negative electrode material 82g, erbium 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, copper) mix well
Ferrite lattice, has obtained the higher composite mixed ferrous acid product salt of purity.
[Co0.5Cu0.3Zn0.2Fe2O4] 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 [Co obtained in example0.5Cu0.3Zn0.2Fe2O4] negative electrode material presentation spherical particle pattern, primary particle is nanoscale
Grain.
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 1.0 and 0.8V, measurement is negative
The volumetric properties of pole material.Cycle performance of battery test: battery made from specific embodiment 1-6 and comparative example 1 is distinguished
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 regulation of cobalt ferrite negative electrode material structural lattice are made in the doping beneficial to metal ion zinc and copper
With significantly improving the volumetric properties and cycle performance of material, especially high rate capability；3) the composite mixed of carbon material has
Conducive to the electric conductivity for improving material, capacity exploitation and high-current leading is promoted to use；4) research also found that the optimization of electrode formulation is shadow
Ring one of the key factor of ferrite electrode performance.Reasonable electrode formulation optimization is the important hand for improving the material overall performance
Section.
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 [CoxCuyZnzFe2O4] or spinel structure ferrite
[CoxCuyZnzFe2O4] constituted with the composite material of carbon material composition, wherein 10,0.7 > z > 0, x+ of > x >=0.3,0.7 > y >
y+z=1；The alkaline secondary cell negative electrode plate includes the active material on cathode matrix and cathode matrix or interior active material
It is prepared by the raw material that following weight percent matches: spinel structure ferrite [CoxCuyZnzFe2O4] negative electrode material or point
Spar type structure ferrite [CoxCuyZnzFe2O4] with carbon material composition composite negative pole material 50%-93.5%, additive 5%-
40%, conductive agent 1%-20% and adhesive solution 0.5%-5%；The additive is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, oxidation
Bismuth, bismuth sulfide, ferrous sulfide, carbonyl iron dust, ferroso-ferric oxide, ferriferrous sulfide, zinc oxide, yttrium oxide, erbium oxide, oxidation are sub-
At least two in tin, ceria, titanium dioxide or staple fiber；The conductive agent is electrically conductive graphite, Ketjen black, conductive charcoal
One of black, carbon nanotube, graphene, oxidation titanous, nickel powder, cobalt powder, copper powder, glass putty are a variety of；The binder is poly-
One of tetrafluoroethene, sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose are a variety of；Institute
Stating cathode matrix is perforated steel ribbon, 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 [CoxCuyZnzFe2O4] with carbon material composition composite material in carbon
Material is crystalline flake graphite, carbon nanotube, graphene, acetylene black, Ketjen black or carbon fiber, the quality hundred of carbon material in composite material
Dividing content 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 spinel structure ferrite [CoxCuyZnzFe2O4] negative electrode material specific synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble cobalt and soluble zinc salt are add to deionized water and are configured to rub
The copper and iron cobalt 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 15-80 DEG C in copper and iron cobalt zinc composite compaction technique, is stirred continuously until and mixes after the reaction was completed
The pH 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 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 [Co after sievingxCuyZnzFe2O4] 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 spinel structure ferrite [CuxZnyNizFe2O4] specific with the composite negative pole material of carbon material composition
Synthesis step are as follows:
(1) soluble copper salt, soluble ferric iron salt, soluble cobalt and soluble zinc salt are add to deionized water and are configured to rub
You are the copper and iron cobalt zinc composite compaction technique of 0.5-7mol/L at concentration, then carbon material is evenly spread to copper and iron cobalt zinc composite compaction technique
In obtain the copper and iron cobalt 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 15-80 DEG C in the copper and iron cobalt zinc composite compaction technique containing carbon material, is stirred continuously until
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 cobalt is cobalt nitrate, cobaltous sulfate, cobalt acetate or cobalt chloride, and the soluble copper salt is
Copper nitrate, copper sulphate, copper acetate or copper chloride, the soluble ferric iron salt are ferric nitrate, ferric sulfate, ferric acetate or iron chloride, institute
Stating soluble zinc salt is zinc nitrate, zinc sulfate, zinc acetate or zinc 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%-93.5%'s
Spinel structure ferrite [CoxCuyZnzFe2O4] negative electrode material or spinel structure ferrite [CoxCuyZnzFe2O4] with
The additive and weight percent proportion that the composite negative pole material of carbon material composition, weight percent proportion are 5%-40% are 1%-20%'s
Conductive agent is uniformly mixed, and is then added in the adhesive solution that weight percent is 0.5%-5%, is stirred evenly, work is made
Property compound paste, then by active material slurry obtained be coated in cathode matrix on, by drying, tabletting, punching, weld pole
Alkaline secondary cell negative electrode plate is made in ear；The additive is nickel sulfate, nickel sulfide, vulcanizes sub- cobalt, bismuth oxide, bismuth sulfide, sulphur
Change ferrous iron, carbonyl iron dust, ferroso-ferric oxide, ferriferrous sulfide, zinc oxide, yttrium oxide, erbium oxide, stannous oxide, ceria,
At least two in titanium dioxide or staple fiber；The conductive agent is electrically conductive graphite, Ketjen black, conductive black, carbon nanotube, stone
One of black alkene, oxidation titanous, nickel powder, cobalt powder, copper powder, 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.
7. a kind of alkaline secondary cell, including battery case and it is located at the intracorporal polar plate group of battery case and electrolyte, wherein pole plate
Group includes positive plate, negative plate and diaphragm, it is characterised in that: the negative plate is using alkali secondary described in claim 1
Cell negative plate.
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| CN110931771A (en) * | 2019-12-10 | 2020-03-27 | 河南创力新能源科技股份有限公司 | Preparation method of high-activity negative electrode material of alkaline secondary battery |
| CN111847526B (en) * | 2020-07-29 | 2021-04-23 | 十堰浩达新能源科技有限公司 | High-capacity super capacitor |
| CN111987292B (en) * | 2020-08-14 | 2022-07-08 | 湖南格瑞普新能源有限公司 | Nickel-hydrogen battery wet method cathode process added with short fibers |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3836397A (en) * | 1972-07-31 | 1974-09-17 | Westinghouse Electric Corp | Iron electrode for alkaline cells |
| CN101651208A (en) * | 2008-12-17 | 2010-02-17 | 成都和能科技有限公司 | Low self-discharge ferrous electrode material |
| CN105457025A (en) * | 2015-12-14 | 2016-04-06 | 大连理工大学 | Preparation method of nanoparticles for self-controlled temperature magnetic-induction hyperthermia |
| CN105514365A (en) * | 2015-12-02 | 2016-04-20 | 常州大学 | Process for preparing lithium ion battery anode material MnFe2O4/rGO with hydrothermal method |
| CN105552331A (en) * | 2015-12-28 | 2016-05-04 | 安泰科技股份有限公司 | Iron-cobalt oxide/graphene composite material, preparation method for composite material and application of composite material |
| CN106654401A (en) * | 2016-11-30 | 2017-05-10 | 湘潭大学 | Bismuth ferrite/nickel hydroxide secondary alkali battery and preparation method therefor |
-
2017
- 2017-09-03 CN CN201710782775.2A patent/CN107658441B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3836397A (en) * | 1972-07-31 | 1974-09-17 | Westinghouse Electric Corp | Iron electrode for alkaline cells |
| CN101651208A (en) * | 2008-12-17 | 2010-02-17 | 成都和能科技有限公司 | Low self-discharge ferrous electrode material |
| CN105514365A (en) * | 2015-12-02 | 2016-04-20 | 常州大学 | Process for preparing lithium ion battery anode material MnFe2O4/rGO with hydrothermal method |
| CN105457025A (en) * | 2015-12-14 | 2016-04-06 | 大连理工大学 | Preparation method of nanoparticles for self-controlled temperature magnetic-induction hyperthermia |
| CN105552331A (en) * | 2015-12-28 | 2016-05-04 | 安泰科技股份有限公司 | Iron-cobalt oxide/graphene composite material, preparation method for composite material and application of composite material |
| CN106654401A (en) * | 2016-11-30 | 2017-05-10 | 湘潭大学 | Bismuth ferrite/nickel hydroxide secondary alkali battery and preparation method therefor |
Non-Patent Citations (1)
| Title |
|---|
| Facile moicrowave synthesis of CoFe2O4 spheres and their application as anode for lithium-ion batteries;Sukeun Yoon;《J Appl Electrochem》;20140817(第44期);第1069-1074页 * |
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