CN107634198A - Alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative material battery - Google Patents

Alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative material battery Download PDF

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CN107634198A
CN107634198A CN201710782788.XA CN201710782788A CN107634198A CN 107634198 A CN107634198 A CN 107634198A CN 201710782788 A CN201710782788 A CN 201710782788A CN 107634198 A CN107634198 A CN 107634198A
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secondary cell
negative electrode
alkaline secondary
alkaline
nickel
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CN107634198B (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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Abstract

The invention discloses a kind of alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative material battery, belong to secondary battery cathode material technical field.Technical scheme main points are:Alkaline secondary cell negative electrode material, by spinel structure ferrite [NixCuyFe2O4] or spinel structure ferrite [NixCuyFe2O4] formed with the composite that carbon material forms, wherein 1 > x >=0.5,0.5 >=y > 0, x+y=1.The invention further particularly discloses the preparation method of the alkaline secondary cell negative electrode material and its application in alkaline secondary cell negative electrode plate.The negative material 0.2C electric discharge gram volumes of the present invention reach 440mAh/g, 5C electric discharge gram volumes reach 350mAh/g, 1C, which circulates 200 capability retentions, can reach more than 90%, and the alkaline secondary cell prepared using the novel anode material has the advantages of higher than energy, specific power is high and has extended cycle life.

Description

Alkaline secondary cell negative electrode material [NixCuyFe2O4] and using the negative 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 Expect [NixCuyFe2O4] and preparation method thereof and using the negative material battery.
Background technology
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 security is good and the particular advantages such as cost performance height, being still widely used in by people various Energy storage device.Due to problem of environmental pollution existing for cadmium cathode, Cd-Ni secondary battery has been restricted at present in commercial market should With.Because 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 problems such as deformation and dendrite being present due to the zinc load that zinc-nickel secondary batteries use, such The cycle life of type battery is poor, it would be highly desirable to improves.The development of iron nickel secondary batteries, it is wide in recent years concerned, however, with four oxidations Passivation always be present and the problem of liberation of hydrogen for the iron negative pole of main active substances in three-iron, cause its high rate performance poor (< 2C) and Active material utilization efficiency is low (actual 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 ripe nickel positive pole, the correlation technique progress of negative pole is clearly to restrict what it developed One key factor.At present, the exploitation of novel anode material is to promote the important means of alkaline secondary cell development, receives section Grind the extensive concern of worker.
The content of the invention
Present invention solves the technical problem that it there is provided a kind of cheap, good rate capability and excellent new of cycle performance Type alkaline secondary cell negative electrode material [NixCuyFe2O4] and preparation method thereof and using the negative material battery.
The present invention is to solve above-mentioned technical problem to adopt the following technical scheme that, alkaline secondary cell negative electrode material, its feature It is by spinel structure ferrite [NixCuyFe2O4] or spinel structure ferrite [NixCuyFe2O4] and carbon material group Into composite form, wherein 1 > x >=0.5,0.5 >=y > 0, x+y=1.
Further limit, the spinel structure ferrite [NixCuyFe2O4] with carbon material composition composite in Carbon material is crystalline flake graphite, CNT, graphene, acetylene black, Ketjen black or carbon fiber, the quality of carbon material in composite 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 [NixCuyFe2O4] the specific synthesis step of negative material is:
(1) soluble nickel salt, soluble copper salt and soluble ferric iron salt are added in deionized water and are configured to molar concentration For 0.5-7mol/L ambrose alloy iron composite compaction technique;
(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 ambrose alloy iron composite compaction technique in 15-80 DEG C, be stirred continuously until after the completion of reaction The pH of mixed liquor is 7-14;
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 5-48h, after being cooled to room temperature, passed through Filter, wash, be dried to obtain brown powder;
(5) under inert nitrogen gas or argon gas atmosphere or air atmosphere, brown powder is heat-treated 1- in 300-800 DEG C 24h, grinding, obtains target product spinel structure ferrite [Ni after sievingxCuyFe2O4] negative 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 [NixCuyFe2O4] with the specific synthesis step of composite negative pole material of carbon material composition be:
(1) soluble nickel salt, soluble copper salt and soluble ferric iron salt are added in deionized water and are configured to molar concentration For 0.5-7mol/L ambrose alloy iron composite compaction technique, then carbon material is evenly spread in ambrose alloy iron composite compaction technique and contained There is the ambrose alloy iron composite compaction technique of 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) in the 15-80 DEG C of ambrose alloy iron composite compaction technique that alkaline solution is added to containing carbon material, lasting stirring is straight The pH of mixed liquor is 7-14 after the completion of to reaction;
(4) mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 5-48h, after being cooled to room temperature, passed through Filter, wash, be dried to obtain black powder;
(5) under inert nitrogen gas or argon gas atmosphere or air atmosphere, black powder is heat-treated 1- in 300-800 DEG C 24h, grinding, obtains target product spinel structure ferrite [Ni after sievingxCuyFe2O4] with carbon material composition Compound Negative Pole material.
Further limit, the soluble nickel salt is nickel nitrate, nickel sulfate, nickel acetate or nickel chloride, 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 chlorination Iron, the alkaline hydrated oxide are sodium hydroxide, potassium hydroxide 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.
Further limit, the alkaline secondary cell negative electrode plate includes on negative pole matrix and negative pole matrix or interior active matter Matter, the raw material that the active material is matched by following weight percent are prepared:Spinel structure ferrite [NixCuyFe2O4] Negative material 50%-93.5%, additive 5%-40%, conductive agent 1%-20% and adhesive solution 0.5%-5% or point Spar type structure ferrite [NixCuyFe2O4] with carbon material composition composite negative pole material 55%-93.5%, 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 concretely comprise the following steps:First will Spinel structure ferrite [the Ni that weight percent proportioning is 50%-93.5%xCuyFe2O4] negative material, weight percent match somebody with somebody The conductive agent for being 1%-20% than the additive for 5%-40% and weight percent proportioning is well mixed or matches weight percent For 55%-93.5% spinel structure ferrite [NixCuyFe2O4] composite negative pole material and again with carbon material composition The additive that amount per distribution ratio is 5%-40% is well mixed, and is then added to bonding of the weight percent proportioning for 0.5%-5% In the agent aqueous solution, stir, active material slurry is made, obtained active material slurry is then coated in negative pole matrix On, by drying, tabletting, punching, soldering polar ear, alkaline secondary cell negative electrode plate is made.
Further limit, the additive be nickel sulfate, nickel sulfide, the sub- cobalt of vulcanization, bismuth oxide, bismuth sulfide, ferrous sulfide, Carbonyl iron dust, ferroso-ferric oxide, ferriferrous sulfide, zinc oxide, yittrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide At least two in titanium or chopped fiber;The conductive agent be electrically conductive graphite, Ketjen black, conductive black, CNT, graphene, Aoxidize the one or more in titanous, nickel powder, cobalt powder, copper powder or glass putty;The binding agent is polytetrafluoroethylene (PTFE), carboxymethyl cellulose One or more in plain sodium, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl methyl cellulose;The negative pole matrix 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 container and the pole plate group being sealed in battery container and electrolysis Liquid, wherein pole plate group include positive plate, negative plate and barrier film, it is characterised in that:The negative plate uses above-mentioned alkali secondary Cell negative plate.
The present invention has the advantages that compared with prior art:Spinel structure ferrite [NixCuyFe2O4] and Its carbon composite greatly improves the structural stability during its charge and discharge cycles by the chanza of copper metal ion And high rate performance, evolving hydrogen reaction are inhibited, the volumetric properties of material are improved.Simultaneously can be further with the compound of carbon material Significantly improve the electric conductivity of electrode, reduce activation polarization, improve the high rate performance and cycle performance of battery.Pass through metallic copper The synergy of element and carbon, and the optimization of electrode formulation, the 0.2C electric discharge gram volumes of the new material can be caused to reach To 440mAh/g, 5C electric discharge gram volumes reach 350mAh/g, and 1C, which circulates 200 capability retentions, can reach more than 90%.Adopt The advantages of alkaline secondary cell prepared with the novel anode material has, good rate capability higher than energy and had extended cycle life.
Brief description of the drawings
Fig. 1 is the XRD of alkaline secondary cell negative electrode material made from embodiment and comparative example;
Fig. 2 is [Ni made from embodiment0.5Cu0.5Fe2O4] negative material SEM figure.
Embodiment
The above of the present invention is described in further details by the following examples, but this should not be interpreted as to this The scope for inventing above-mentioned theme is only limitted to following embodiment, and all technologies realized based on the above of the present invention belong to this hair Bright scope.
Embodiment 1
[Ni0.90Cu0.1Fe2O4] negative material preparation:
Nickel sulfate, copper chloride and iron chloride are added in deionized water for Ni/Cu/Fe=0.9/0.1/2 in molar ratio It is configured to the ambrose alloy iron composite compaction technique that total mol concentration is 2mol/L;Sodium hydroxide is dissolved in deionized water and is configured to mole Concentration is 4mol/L sodium hydroxide solution;Sodium hydroxide solution is added in ambrose alloy iron composite compaction technique in 40 DEG C and adjusted The pH of mixed liquor is 12, persistently stirs 30min;Mixed liquor is transferred in hydrothermal reaction kettle in 120 DEG C of hydro-thermal reaction 10h, cooling To room temperature, filtered, washing, in 80 DEG C of dry 5h brown powder is obtained;In air atmosphere, by brown powder in 600 DEG C 2h is heat-treated, grinding, target product [Ni is obtained after sieving0.90Cu0.1Fe2O4] negative material.
[Ni0.90Cu0.1Fe2O4] negative material application:
By [the Ni of synthesis0.90Cu0.1Fe2O4] negative material 84g, the black 10g of ferrous sulfide 5g, Ke Qin, mass concentration be The PTFE aqueous solution that the poly-vinyl alcohol solution 0.5g and mass concentration that 2.5% CMC solution 1g, mass concentration are 4% are 60% 0.3g is well mixed, and cathode size is made, and is applied to by coating-spreading mould on steel band both sides, by drying, roll-in, is cut and is made Negative plate.Folder across alkaline battery separator, it will be fitted into special simulated battery shell between sintering positive plate and negative plate, and inject matter The KOH that concentration is 30% and the LiOH electrolyte that mass concentration is 2% are measured, is assembled into the alkaline secondary cell of semitight.
Embodiment 2
[Ni0.8Cu0.2Fe2O4] negative material preparation:
Nickel sulfate, copper nitrate and iron chloride are added in deionized water for Ni/Cu/Fe=0.8/0.2/2 in molar ratio It is configured to the ambrose alloy iron composite compaction technique that total mol concentration is 4mol/L;Potassium hydroxide is dissolved in deionized water and is configured to mole Concentration is 7mol/L potassium hydroxide solution;Potassium hydroxide solution is added in ambrose alloy iron composite compaction technique in 30 DEG C and adjusted The pH of mixed liquor is 14, persistently stirs 10min;Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 8h, cooling To room temperature, filtered, washing, in 80 DEG C of dry 5h brown powder is obtained;In a nitrogen atmosphere, by brown powder in 650 DEG C 2h is heat-treated, grinding, target product [Ni is obtained after sieving0.8Cu0.2Fe2O4] negative material.
[Ni0.8Cu0.2Fe2O4] negative material application:
By [the Ni of synthesis0.8Cu0.2Fe2O4] negative material 82g, bismuth sulfide 5g, cerium oxide 5g, CNT 5g, nickel powder The poly-vinyl alcohol solution 0.3g and mass concentration that HPMC solution 1.2g that 5g, mass concentration are 2.5%, mass concentration are 4% be 60% PTFE aqueous solution 0.2g is well mixed, and cathode size is made, is applied to by coating-spreading mould on Foamed Nickel both sides, is passed through Drying, roll-in, cut negative plate is made.Folder across alkaline battery separator, it will load special between sintering positive plate and negative plate In simulated battery shell, LiOH electrolyte that KOH and mass concentration that implantation quality concentration is 30% are 2% is assembled into semitight Alkaline secondary cell.
Embodiment 3
[Ni0.7Cu0.3Fe2O4] negative material preparation:
Nickel chloride, copper nitrate and iron chloride are added in deionized water for Ni/Cu/Fe=0.7/0.3/2 in molar ratio It is configured to the ambrose alloy iron composite compaction technique that total mol concentration is 1mol/L;Potassium hydroxide is dissolved in deionized water and is configured to mole Concentration is 2mol/L potassium hydroxide solution;Potassium hydroxide solution is added in ambrose alloy iron composite compaction technique in 45 DEG C and adjusted The pH of mixed liquor is 14, persistently stirs 40min;Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 20h, cooling To room temperature, filtered, washing, in 80 DEG C of dry 5h brown powder is obtained;In air atmosphere, by brown powder in 650 DEG C 1h is heat-treated, grinding, target product [Ni is obtained after sieving0.7Cu0.3Fe2O4] negative material.
[Ni0.7Cu0.3Fe2O4] negative material application:
By [the Ni of synthesis0.7Cu0.3Fe2O4] negative material 75g, ferrous sulfide 10g, zinc oxide 5g, crystalline flake graphite 8g, tin The PTFE aqueous solution 0.2g that the HPMC solution 1.4g and mass concentration that powder 3g, mass concentration are 2.5% are 60% is well mixed, system Into cathode size, it is applied to by coating-spreading mould on Foamed Nickel both sides, by drying, roll-in, cuts negative plate is made.Will sintering Folder is fitted into special simulated battery shell, implantation quality concentration is 30% across alkaline battery separator between positive plate and negative plate KOH and LiOH electrolyte that mass concentration is 2%, be assembled into the alkaline secondary cell of semitight.
Embodiment 4
[Ni0.6Cu0.4Fe2O4] negative material preparation:
Nickel sulfate, copper nitrate and ferric nitrate are added in deionized water for Ni/Cu/Fe=0.6/0.4/2 in molar ratio It is configured to the ambrose alloy iron composite compaction technique that total mol concentration is 3.5mol/L;Potassium hydroxide is dissolved in deionized water and is configured to rub The potassium hydroxide solution that your concentration is 3.5mol/L;Potassium hydroxide solution is added in ferronickel copper composite compaction technique in 25 DEG C The pH for adjusting mixed liquor is 10, persistently stirs 30min;Mixed liquor is transferred in hydrothermal reaction kettle in 140 DEG C of hydro-thermal reaction 25h, After being cooled to room temperature, filtered, washing, in 80 DEG C of dry 5h brown powder is obtained;In a nitrogen atmosphere, by brown powder in 750 DEG C of heat treatment 2h, grinding, obtain target product [Ni after sieving0.6Cu0.4Fe2O4] negative material.
[Ni0.6Cu0.4Fe2O4] negative material application:
By [the Ni of synthesis0.6Cu0.4Fe2O4] negative material 78g, ceria 3g, erbium oxide 5g, ferrous sulfide 5g, acetylene The PTFE aqueous solution 0.2g that the poly-vinyl alcohol solution 1.5g and mass concentration that black 5g, Ketjen black 5g, mass concentration are 4% are 60% It is well mixed, cathode size is made, is applied to by coating-spreading mould on Foamed Nickel both sides, by drying, roll-in, cut be made it is negative Pole plate.Folder across alkaline battery separator, it will be fitted between sintering positive plate and negative plate in special simulated battery shell, implantation quality The LiOH electrolyte that the KOH and mass concentration that concentration is 30% are 2%, it is assembled into the alkaline secondary cell of semitight.
Embodiment 5
[Ni0.5Cu0.5Fe2O4] negative material preparation:
Nickel sulfate, copper sulphate and ferric sulfate are added in deionized water for Ni/Cu/Fe=0.5/0.5/2 in molar ratio It is configured to the ambrose alloy iron composite compaction technique that total mol concentration is 3mol/L;Potassium hydroxide is dissolved in deionized water and is configured to mole Concentration is 2mol/L potassium hydroxide solution;Sodium hydroxide solution is added to adjust in ambrose alloy iron composite compaction technique in 25 DEG C and mixed The pH for closing liquid is 12, persistently stirs 30min;Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 15h, is cooled to After room temperature, filtered, washing, in 80 DEG C of dry 5h brown powder is obtained;In air atmosphere, by brown powder in 600 DEG C of heat 10h is handled, grinding, target product [Ni is obtained after sieving0.5Cu0.5Fe2O4] negative material.
[Ni0.5Cu0.5Fe2O4] negative material application:
By [the Ni of synthesis0.5Cu0.5Fe2O4] negative material 65g, ferriferrous sulfide 10g, ferrous sulfide 5g, erbium oxide 2g, The PTFE aqueous solution 0.2g mixing that the HPMC solution 1.4g and mass concentration that superconduction carbon black 5g, mass concentration are 2.5% are 60% Uniformly, cathode size is made, is applied to by coating-spreading mould on foam copper both sides, by drying, roll-in, cuts negative pole is made Plate, folder between sintering positive plate and negative plate across alkaline battery separator, is fitted into special simulated battery shell, implantation quality is dense The LiOH electrolyte for being 2% for 30% KOH and mass concentration is spent, is assembled into the alkaline secondary cell of semitight.
Embodiment 6
[Ni0.5Cu0.5Fe2O4The preparation of]/crystalline flake graphite composite negative pole material:
Nickel sulfate, copper chloride and ferric sulfate are added in deionized water for Ni/Cu/Fe=0.5/0.5/2 in molar ratio It is configured to total mol concentration and is 5mol/L ambrose alloy iron composite compaction technique, then a certain amount of crystalline flake graphite is dispersed with stirring ambrose alloy The ambrose alloy iron composite compaction technique containing carbon material is obtained in iron composite compaction technique, controls the carbon content of final sample 10%, will Potassium hydroxide is dissolved in the potassium hydroxide solution for being configured to that molar concentration is 5mol/L in deionized water;It is in 20 DEG C that potassium hydroxide is molten The pH that liquid is added to regulation mixed liquor in the ambrose alloy iron composite compaction technique containing carbon material is 13, persistently stirs 40min;Will mixing Liquid is transferred in hydrothermal reaction kettle in 170 DEG C of hydro-thermal reaction 18h, after being cooled to room temperature, filtered, washing, is obtained in 80 DEG C of dry 5h To black powder;In a nitrogen atmosphere, black powder is heat-treated 1h in 700 DEG C, grinding, target product is obtained after sieving [Ni0.5Cu0.5Fe2O4]/crystalline flake graphite composite negative pole material.
[Ni0.5Cu0.5Fe2O4The application of]/crystalline flake graphite composite negative pole material:
By [the Ni of synthesis0.5Cu0.5Fe2O4]/crystalline flake graphite composite negative pole material 62g, ferrous sulfide 10g, 5 grams of zinc oxide, Ceria 5g and the poly-vinyl alcohol solution 1.5g that mass concentration is 4% are well mixed, and cathode size is made, passes through coating-spreading mould It is applied on Foamed Nickel both sides, by drying, roll-in, cuts negative plate is made.Will sintering positive plate and negative plate between folder every Alkaline battery separator, is fitted into special simulated battery shell, the KOH and mass concentration that implantation quality concentration is 30% are 2% LiOH electrolyte, it is assembled into the alkaline secondary cell of semitight.
Comparative example 1
[NiFe2O4] negative material preparation:
Nickel sulfate and iron chloride are added in deionized water for Ni/Fe=1/2 in molar ratio and are configured to total mol concentration For 2mol/L ferronickel composite compaction technique;Potassium hydroxide is dissolved in the hydrogen for being configured to that molar concentration is 5mol/L in deionized water Potassium oxide solution;It is 13 to be added to potassium hydroxide solution in 20 DEG C and the pH of mixed liquor is adjusted in ferronickel composite compaction technique, is continued Stir 30min;Mixed liquor is transferred in hydrothermal reaction kettle in 160 DEG C of hydro-thermal reaction 24h, it is filtered, wash after being cooled to room temperature Wash, obtain brown powder in 80 DEG C of dry 5h;Under inert nitrogen gas atmosphere, brown powder is heat-treated 2h in 650 DEG C, Grinding, obtains target product [ZnFe after sieving2O4] negative material.
[NiFe2O4] negative material application:
By [the NiFe of synthesis2O4] negative material 82g, bismuth sulfide 5g, ferriferrous sulfide 5g, superconduction carbon black 5g, mass concentration The PTFE aqueous solution 0.2g that HPMC solution 1.4g and mass concentration for 2.5% are 60% is well mixed, and cathode size is made, and is led to Cross coating-spreading mould to be applied on Foamed Nickel both sides, by drying, roll-in, cut negative plate is made.Will sintering positive plate and negative pole Folder is fitted into special simulated battery shell, KOH and the quality that implantation quality concentration is 30% across alkaline battery separator between plate Concentration is 2% LiOH electrolyte, is assembled into the alkaline secondary cell of semitight.
Sample segment characterizes:
The XRD diffraction test results of portioned product are as shown in figure 1, by Fig. 1 and nickel ferrite based magnetic loaded 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 copper is mixed with ferrite well Lattice, the higher Copper-cladding Aluminum Bar nickel ferrite based magnetic loaded product of purity is obtained.
[Ni0.5Cu0.5Fe2O4] negative material SEM test results it is as shown in Figure 2.By Fig. 2 it can be seen that, above-described embodiment In obtained [Ni0.5Cu0.5Fe2O4] negative material presentation spheric granules pattern, primary particle is nano-scale particle.
Battery performance test:
Volume test:By the simulated battery prepared using specific embodiment 1-6 and comparative example 1 after 0.2C is activated, 0.2C Charge 6h, and battery shelves 30min afterwards, is then discharged to voltage respectively as 1.0V and 0.6V using 0.2C and 5C, determines negative pole material The volumetric properties of material.Cycle performance of battery is tested:By battery made from specific embodiment 1-6 and comparative example 1 respectively in 25 DEG C of rings 1C charge-discharge tests are carried out at a temperature of border, are circulated 200 times.
Battery electrical property test result is listed in table 1.
The battery charging/discharging performance testing of table 1
Can be seen that from above test result has higher gram volume, excellent using the negative material for preparing of the present invention High rate performance and cyclical stability, the requirement of commercial cells, particularly high power capacity high-power battery can be met.These performances Improvement be mainly due to:1) the capacity exploitation of the optimization of synthetic method, especially including high temperature processes to sample is played to pass Important effect;2) modification and regulating and controlling effect of the doping of beneficial copper ion to nickel ferrite based magnetic loaded negative material structural lattice, greatly Improve the volumetric properties and cycle performance of material, especially high rate capability;3) the composite mixed of carbon material is advantageous to improve The electric conductivity of material, promote capacity exploitation and high current application;4) research also found, the optimization of electrode formulation is to influence ferrite One of key factor of electrode performance.Rational electrode formulation optimization is to improve the important means of the material overall performance.
Embodiment above describes the general principle of the present invention, main features and advantages.The technical staff of the industry should Understand, the present invention is not limited to the above embodiments, the original for simply illustrating the present invention described in above-described embodiment and specification Reason, under the scope for not departing from the principle of the invention, various changes and modifications of the present invention are possible, and these changes and improvements are each fallen within In the scope of protection of the invention.

Claims (10)

1. alkaline secondary cell negative electrode material, it is characterised in that by spinel structure ferrite [NixCuyFe2O4] or spinelle Type structure ferrite [NixCuyFe2O4] formed with the composite that carbon material forms, wherein 1 > x >=0.5,0.5 >=y > 0, x+ y=1。
2. alkaline secondary cell negative electrode material according to claim 1, it is characterised in that:The spinel structure ferrous acid Salt [NixCuyFe2O4] with carbon material composition composite in carbon material be crystalline flake graphite, CNT, graphene, acetylene Black, Ketjen black or carbon fiber, the weight/mass percentage composition of carbon material is 0.1%-20% in composite.
A kind of 3. preparation method of the alkaline secondary cell negative electrode material described in claim 1, it is characterised in that spinel-type knot Structure ferrite [NixCuyFe2O4] the specific synthesis step of negative material is:
(1)Soluble nickel salt, soluble copper salt and soluble ferric iron salt are added in deionized water and is configured to molar concentration and is 0.5-7mol/L ambrose alloy iron composite compaction technique;
(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 ambrose alloy iron composite compaction technique in 15-80 DEG C, is stirred continuously until after the completion of reacting and mixes The pH of liquid is 7-14;
(4)Mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 5-48h, after being cooled to room temperature, filtered, Wash, be dried to obtain brown powder;
(5)Under inert nitrogen gas or argon gas atmosphere or air atmosphere, brown powder is heat-treated 1-24h in 300-800 DEG C, Grinding, obtains target product spinel structure ferrite [Ni after sievingxCuyFe2O4] negative material.
A kind of 4. preparation method of the alkaline secondary cell negative electrode material described in claim 1, it is characterised in that spinel-type knot Structure ferrite [NixCuyFe2O4] with the specific synthesis step of composite negative pole material of carbon material composition be:
(1)Soluble nickel salt, soluble copper salt and soluble ferric iron salt are added in deionized water and is configured to molar concentration and is 0.5-7mol/L ambrose alloy iron composite compaction technique, then carbon material is evenly spread in ambrose alloy iron composite compaction technique and obtained containing carbon The ambrose alloy iron composite compaction technique of 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)In the ambrose alloy iron composite compaction technique that 15-80 DEG C is added to alkaline solution containing carbon material, it is stirred continuously until anti- The pH of mixed liquor is 7-14 after the completion of answering;
(4)Mixed liquor is transferred in hydrothermal reaction kettle in 100-180 DEG C of hydro-thermal reaction 5-48h, after being cooled to room temperature, filtered, Wash, be dried to obtain black powder;
(5)Under inert nitrogen gas or argon gas atmosphere or air atmosphere, black powder is heat-treated 1-24h in 300-800 DEG C, Grinding, obtains target product spinel structure ferrite [Ni after sievingxCuyFe2O4] with carbon material composition composite negative pole material Material.
5. the preparation method of the alkaline secondary cell negative electrode material according to claim 3 or 4, it is characterised in that:It is described can Insoluble nickel salt is nickel nitrate, nickel sulfate, nickel acetate or nickel chloride, the soluble copper salt be copper nitrate, copper sulphate, copper acetate or Copper chloride, the soluble ferric iron salt are ferric nitrate, ferric sulfate, ferric acetate or iron chloride, and the alkaline hydrated oxide is hydroxide Sodium, potassium hydroxide or lithium hydroxide.
A kind of 6. alkaline secondary cell negative electrode plate, it is characterised in that:The alkaline secondary cell negative electrode plate includes claim 1 Or the alkaline secondary cell negative electrode material described in 2.
7. the alkaline secondary cell negative electrode plate according to right 6, it is characterised in that:The alkaline secondary cell negative electrode plate includes On negative pole matrix and negative pole matrix or interior active material, the raw material that the active material is matched by following weight percent prepare and Into:Spinel structure ferrite [NixCuyFe2O4] negative material 50%-93.5%, additive 5%-40%, conductive agent 1%-20% With adhesive solution 0.5%-5% or spinel structure ferrite [NixCuyFe2O4] with carbon material composition composite negative pole material Expect 55%-93.5%, additive 5%-40% and adhesive solution 0.5%-5%.
A kind of 8. preparation method of the alkaline secondary cell negative electrode plate described in claim 6 or 7, it is characterised in that specific steps For:Spinel structure ferrite [Ni first by weight percent proportioning for 50%-93.5%xCuyFe2O4] negative material, weight The conductive agent that additive and the weight percent proportioning that per distribution ratio is 5%-40% are 1%-20% is well mixed or matches somebody with somebody weight percent Than the spinel structure ferrite [Ni for 55%-93.5%xCuyFe2O4] with carbon material composition composite negative pole material and weight Per distribution ratio is that 5%-40% additive is well mixed, and it is water-soluble for 0.5%-5% binding agent to be then added to weight percent proportioning In liquid, stir, active material slurry is made, then pass through obtained active material slurry coated on negative pole matrix Drying, tabletting, punching, soldering polar ear, alkaline secondary cell negative electrode plate is made.
9. the preparation method of alkaline secondary cell negative electrode plate according to claim 8, it is characterised in that:The additive is Nickel sulfate, nickel sulfide, the sub- cobalt of vulcanization, bismuth oxide, bismuth sulfide, ferrous sulfide, carbonyl iron dust, ferroso-ferric oxide, ferriferrous sulfide, At least two in zinc oxide, yittrium oxide, erbium oxide, stannous oxide, ceria, titanium dioxide or chopped fiber;The conduction Agent is in electrically conductive graphite, Ketjen black, conductive black, CNT, graphene, oxidation titanous, nickel powder, cobalt powder, copper powder or glass putty One or more;The binding agent is polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber, polyvinyl alcohol or hydroxypropyl One or more in methylcellulose;The negative pole matrix be perforated steel ribbon, 3 D stereo steel band, stainless (steel) wire, Foamed Nickel, Foam copper, foaming iron or copper mesh.
10. a kind of alkaline secondary cell, including battery container and pole plate group and electrolyte in battery container, wherein pole plate Group includes positive plate, negative plate and barrier film, it is characterised in that:The negative plate is using the alkali secondary described in claim 6 or 7 Cell negative plate.
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