CN108963225A - A kind of Ni3S2/ MnO composite material and preparation method and the application in aqueous alkaline battery - Google Patents

A kind of Ni3S2/ MnO composite material and preparation method and the application in aqueous alkaline battery Download PDF

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CN108963225A
CN108963225A CN201810779629.9A CN201810779629A CN108963225A CN 108963225 A CN108963225 A CN 108963225A CN 201810779629 A CN201810779629 A CN 201810779629A CN 108963225 A CN108963225 A CN 108963225A
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mno
composite material
carbon paper
preparation
mno composite
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CN108963225B (en
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杨剑
张隽殊
张大鹏
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Shandong University
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Shandong 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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 present invention relates to a kind of Ni3S2/ MnO composite material and preparation method and the application in aqueous alkaline battery, the Ni3S2/ MnO compound is that load has Ni on carbon paper3S2/ MnO active material, Ni3S2/ MnO active material shape is cauliflower shape, and active material loading is 1.5~8mgcm‑2.By simple electro-deposition method, presoma is generated in carbon paper previous step, obtains final product Ni after then calcining3S2/ MnO compound.Obtained composite material large specific surface area promotes the high rate performance and cyclical stability of material.In the test of aqueous alkaline battery applications, Ni3S2/ MnO composite material presents excellent high rate performance, in 15A g‑1Current density under still have 30mAh g‑1Specific discharge capacity；Good cyclical stability is shown during long circulating charge-discharge test, in 2A g‑1Current density under after charge and discharge 450 times, specific capacity can still keep 85.1mAh g‑1, it is equivalent to the 97.5% of initial specific capacities, and maintained in the whole process close to absolutely coulombic efficiency.

Description

A kind of Ni3S2/ MnO composite material and preparation method in aqueous alkaline battery Using
Technical field:
The present invention relates to a kind of Ni3S2/ MnO composite material and preparation method and the application in aqueous alkaline battery, belong to In electrochemical technology field.
Background technique:
Lithium ion battery substantially increases people's lives quality since capacity is big, high-efficient, brings many conveniences. Consequent is the news of more and more battery explosions, burning, and people start the safety to lithium ion battery and generate worry And query.Inflammable and explosive electrolyte, harsh assembled condition and high cost of material, all force people that sight is started to throw To other kinds of energy storage device.Water system battery replaces existing widely used organic electrolyte, water system battery tool using aqueous solution There are the advantages such as low cost, high safety performance, problem above can be efficiently solved.Since aqueous solution possesses better ionic conduction Performance, this allows water system battery to obtain higher power density.
From 1994 first with LiMn2O4For positive active material, VO2For the aquo-lithium ion battery of negative electrode active material Research report come out since, people are made that huge effort in terms of water system lithium/sodium-ion battery, also achieve huge It breaks through.In recent years, researchers have found LiFePO successively4,LiTi2(PO4)3,Na0.44MnO2Etc. water systems electrode material, but this Utilization cannot be mass produced in a little materials, and distance realizes that large-scale commercial applications apply also very long distance.Therefore, many researchers Sight has been rotated back into again and has been realized in commercialized battery.
In commercial water system battery existing at present, highest market occupancy is lead-acid battery and Ni-Zn battery.Plumbic acid Battery remains leader's posture due to mature preparation process in World Battery Market.And alkalinity Ni-Zn battery by It is up to 1.8V in output voltage, it is more competitive than lead-acid battery in energy density and power density.But existing business Ni-Zn battery generallys use β-Ni (OH)2As positive electrode, it cycle life, in terms of be also unable to satisfy The demand of people, this is also the main reason that alkaline Ni-Zn battery lags behind lead-acid battery.
In recent years in addition to being directed to Ni (OH)2Study on the modification outside, also there is researcher to turn one's attention to other materials, nickel Base sulfide is exactly outstanding person therein.This is primarily due to compared to oxide, and Ni-based sulfide possesses better electronics conduction Rate, especially Ni3S2.But Ni at present3S2In terms of research it is more, as aqueous alkaline anode material The report of material is considerably less.Although Ni3S2Electric conductivity it is preferable, but the chemical property of the material can not be with carbon material and metal Conductor is compared, currently, usually having the material progress of high conductivity compound itself and carbon material, nickel foam etc.；Or pass through structure The means such as special pattern are built to further increase Ni3S2Chemical property.(referring to ElectrochimicaActa 2017, 251,235；Adv.Energy Mater.2017,7,1700983；J.Mater.Chem.A 2015,3,16150), although passing through Recombination energy can improve chemical property to a certain extent, but chemical property is not still high, and current complex method is complicated, Obtained composite material is unstable.
Summary of the invention:
In view of the deficiencies of the prior art, the present invention provides a kind of Ni3S2/ MnO composite material and preparation method in water system Application in alkaline battery.
Summary of the invention:
The present invention is generated Ni-Mn presoma in carbon paper previous step, is further calcined by simple electro-deposition method After obtain Ni3S2/ MnO compound, Ni3S2/ MnO compound is that load has Ni on carbon paper3S2/ MnO active material, Ni3S2/ MnO is living Property substance be cauliflower shape, by the compound aqueous alkaline battery applications test in, Ni3S2/ MnO composite material presents excellent Different high rate performance, in 15Ag-1Current density under still have 30mAh g-1Specific discharge capacity；In long circulating charge-discharge test Good cyclical stability is shown in the process, in 2A g-1Current density under after charge and discharge 450 times, specific capacity can still be kept 85.1mAh g-1, it is equivalent to the 97.5% of initial specific capacities, and maintained in the whole process close to absolutely coulomb Efficiency.
Technical scheme is as follows:
A kind of Ni3S2/ MnO composite material, the Ni3S2/ MnO compound is that load has Ni on carbon paper3S2/ MnO activity Substance, Ni3S2/ MnO active material shape is cauliflower shape, and active material loading is 1.5~8mgcm-2。
It is further preferred that active material loading is 4mgcm-2。
Ni of the invention3S2/ MnO composite material is that material precursor is carried on carbon paper conduction afflux by electro-plating method On body, high temperature sintering is then carried out, obtains the active material that load on carbon paper has cauliflower pattern, no conductive black and binder It is added.Reduce between material granule and particle, the interface resistance between particle and conductive current collector；Reduce the useless matter of electrode The specific gravity of amount increases the commercialized possibility of material.
Above-mentioned Ni3S2The preparation method of/MnO composite material, comprises the following steps that
With NiCl2、MnCl2Carbon paper surface electro-deposition is made by electro-deposition method for electrolyte with the mixed solution of thiocarbamide Active material obtains forerunner's product, the then high-temperature calcination under inert atmosphere obtains Ni after washing is dry3S2/ MnO composite material.
It is preferred according to the present invention, NiCl in mixed solution2Concentration be 3~15mmol L-1, MnCl2Concentration be 2.5 ~10mmol L-1, the concentration of thiocarbamide is 0.25~1mol L-1。
It is further preferred that NiCl in mixed solution2Concentration be 7.5mmol L-1, MnCl2Concentration be 5mmol L-1, The concentration of thiocarbamide is 0.5mol L-1。
Preferred according to the present invention, electro-deposition voltage is -0.8V~-0.9V constant voltage, and electrodeposition time is 30min-120min。
Highly preferred, electro-deposition voltage is the constant voltage of -0.85V, electrodeposition time 60min.
Preferred according to the present invention, during electro-deposition, carbon paper is working electrode, gauze platinum electrode be to electrode, it is sweet Mercury electrode is reference electrode.
Preferred according to the present invention, the inert atmosphere is Ar gas, and high-temperature calcination temperature is 350-550 DEG C, when calcining Between be 1~3 hour.
It is further preferred that high-temperature calcination temperature is 400 DEG C, calcination time is 2 hours.
A currently preferred technical solution, Ni3S2The preparation method of/MnO composite material, comprises the following steps that
With NiCl2、MnCl2Mixed solution with thiocarbamide is electrolyte, carries out electricity to carbon paper under the constant potential of -0.85V Deposition obtains forerunner's product, then under Ar atmosphere, at 400 DEG C after keeping carbon paper surface electro-deposition active material, washing dry Calcining 2 hours, obtains Ni3S2/ MnO composite material.
Preferred according to the present invention, the carbon fiber diameter of carbon paper is 7-9 μm.
Above-mentioned Ni3S2The application of/MnO composite material is applied in water aqueous alkaline battery, uses as positive electrode.
The principle of the present invention:
It is collector that the present invention, which selects carbon paper, and basic composed structure-carbon fiber of carbon paper, diameter is about 8 μm.Its table Face is more coarse, can come into full contact with electrolyte in electrodeposition process, and provides biggish surface area so as to Ni3S2/ MnO attachment.And the electric conductivity that carbon fiber is excellent, be conducive to charge in the transmitting of electrolyte and carbon paper surface, so that electro-deposition Electrochemical reaction in journey is gone on smoothly.In addition, not binder obstruction but also electronics collector and active material it Between transmission efficiency it is higher so that the General Promotion of battery high rate performance and cyclical stability.The presence of MnO makes forerunner simultaneously The pattern of material in the plating process becomes fluffy and is tightly wrapped in carbon fiber surface, reduces exposed carbon fiber and aqueous solution It directly contacts, reduces the rate of battery analysis oxygen, ensure that the high coulombic efficiency during circulating battery.
Ni of the invention3S2/ MnO composite material has following outstanding feature:
(1) present invention generates presoma in carbon paper previous step by simple electro-deposition method, after further calcining Obtain final product Ni3S2/ MnO compound.In the test of aqueous alkaline battery applications, Ni3S2/ MnO composite material presents excellent Different high rate performance, in 15A g-1Current density under still have 30mAh g-1Specific discharge capacity；In long circulating charge-discharge test Good cyclical stability is shown in the process, in 2A g-1Current density under after charge and discharge 450 times, specific capacity can still be kept 85.1mAh g-1, it is equivalent to the 97.5% of initial specific capacities, and maintained in the whole process close to absolutely coulomb Efficiency.
(2) precursor material is directly carried on collector, by a step electroplating reaction then through too short by material of the present invention The sintering of temporary high temperature, it is simple and easy to operate.
(3) pattern of the invention is graininess cauliflower pattern, and large specific surface area has shown excellent in battery testing High rate performance and cyclical stability.
(4) addition of the invention without conductive black and binder, reduces between material granule and particle, particle and conduction Interface resistance between collector；The specific gravity for reducing the useless quality of electrode increases the commercialized possibility of material.
Detailed description of the invention:
Fig. 1 is Ni made from the embodiment of the present invention 13S2/ MnO composite material (S1) and presoma of the comparative example 1 without sintering Material (S2) and 2 electroplate liquid of comparative example are free of Mn2+Obtained pure Ni3S2The XRD comparison diagram of material (S3).
Fig. 2 is Ni made from the embodiment of the present invention 13S2/ MnO composite material (S1) and presoma of the comparative example 1 without sintering Material (S2) and 2 electroplate liquid of comparative example are free of Mn2+Obtained pure Ni3S2Material (S3) stereoscan photograph.Wherein, a, b Figure is cauliflower pattern Ni3S2The stereoscan photograph of/MnO composite material (S1), c, d figure are forerunner of the comparative example 1 without sintering The stereoscan photograph of body material (S2) material, e, f figure are 2 electroplate liquid of comparative example without Mn2+Obtained pure Ni3S2Material (S3) stereoscan photograph.
Fig. 3 is Ni made from the embodiment of the present invention 13S2/ MnO composite material (S1) and presoma of the comparative example 1 without sintering The element mapping graph of material (S2).Wherein, a is cauliflower pattern Ni3S2The element mapping graph of/MnO composite material (S1), b are not The element mapping graph of persursor material (S2) through being sintered.
Fig. 4 is Ni made from the embodiment of the present invention 13S2/ MnO composite material (S1) cyclic voltammetry curve, charging and discharging curve, High rate performance and in 2A g-1Cycle performance figure under current density.Wherein, a figure is cyclic voltammetry curve figure, and b figure is charge and discharge Curve graph, c figure are high rate performance figure, and d figure is that current density is 2A g-1When cycle performance figure.
Fig. 5 is persursor material (S2) cyclic voltammetry curve, charging and discharging curve, high rate performance of the comparative example 1 without sintering With in 2A g-1Cycle performance figure under current density.Wherein, a figure is cyclic voltammetry curve figure, and b figure is charging and discharging curve figure, c Figure is that current density is 10A g-1When cycle performance figure.
Fig. 6 is 2 electroplate liquid of comparative example without Mn2+Obtained pure Ni3S2Material (S3) cyclic voltammetry curve, charge and discharge are bent Line, high rate performance and in 2A g-1Cycle performance figure under current density.Wherein, a figure is cyclic voltammetry curve figure, and b figure is charge and discharge Electric curve graph, c figure are high rate performance figure, and d figure is that current density is 2A g-1When cycle performance figure.
Specific embodiment:
The present invention will be described in more detail with reference to the accompanying drawings and examples.
Raw material in embodiment is commercial products.
Embodiment 1
Ni3S2The preparation method of/MnO composite material, comprises the following steps that
With NiCl2、MnCl2Mixed solution with thiocarbamide is electrolyte, NiCl in mixed solution2Concentration be 7.5mmol L-1, MnCl2Concentration be 5mmol L-1, the concentration of thiocarbamide is 0.5mol L-1, under the constant potential of -0.85V to carbon paper into Row electro-deposition 60min obtains forerunner's product after keeping carbon paper surface electro-deposition active material, washing dry, then under Ar atmosphere, It is calcined 2 hours at 400 DEG C, obtains Ni3S2/ MnO composite material (S1).Active material quality on carbon paper is 4mg cm-2。
Ni obtained3S2The XRD diagram and scanning electron microscope of/MnO composite material (S1) are as shown in Figure 1 and Figure 2, can be with by Fig. 2 Find out, which is presented graininess combination cauliflower shape and densification is coated on carbon fiber surface, and XRD test is respectively provided with Carbon paper, Ni3S2With three kinds of different characteristic peaks of MnO, Mn element can be observed in element mapping.
Comparative example 1
The preparation method of persursor material (S2) without sintering, comprises the following steps that
With NiCl2、MnCl2Mixed solution with thiocarbamide is electrolyte, NiCl in mixed solution2Concentration be 7.5mmol L-1, MnCl2Concentration be 5mmol L-1, the concentration of thiocarbamide is 0.5mol L-1, under the constant potential of -0.85V to carbon paper into Row electro-deposition 60min makes carbon paper surface electro-deposition active material, obtains persursor material (S2).Active material quality on carbon paper For 4mg cm-2。
The XRD diagram and scanning electron microscope of persursor material (S2) obtained without sintering are as shown in Figure 1 and Figure 2, pass through Fig. 2 As can be seen that cauliflower shape is presented for the material morphology and densification is coated on carbon fiber surface, XRD test is only with the spy of carbon paper Peak is levied, Mn element can be observed in element mapping.
Comparative example 2
Electroplate liquid is free of Mn2+Obtained pure Ni3S2The preparation method of material (S3), comprises the following steps that
With NiCl2Mixed solution with thiocarbamide is electrolyte, NiCl in mixed solution2Concentration be 7.5mmol L-1, sulphur The concentration of urea is 0.5mol L-1, electro-deposition 60min is carried out to carbon paper under the constant potential of -0.85V.After a period of time, washing It is dry, forerunner's product is obtained, then in 400 DEG C of calcinings, 2 hours (Ar atmosphere), obtains final product (S3).Active matter on carbon paper Matter quality is 4mg cm-2。
Obtained Ni3S2The XRD diagram and scanning electron microscope of material (S3) are as shown in Figure 1 and Figure 2, as seen in Figure 2, the material Material pattern is presented nano flower shape and is simultaneously coated on carbon fiber surface, but coat it is not fine and close enough, XRD test be respectively provided with carbon paper and Ni3S2Two kinds of different characteristic peaks.
Performance test
One, to cauliflower pattern Ni made from embodiment 13S2Before/MnO composite material (S1) and comparative example 1 are without sintering It drives body material (S2) and 2 electroplate liquid of comparative example is free of Mn2+Obtained pure Ni3S2Material (S3) sample does XRD test, spreads out Style is penetrated as shown in Figure 1, three kinds of materials all have the characteristic peak of carbon paper it can be seen from Fig. 1, shows that its collector is carbon Paper and in the whole process there is no decompose or object mutually change.And for S1 sample, it is compared with its presoma S2 sample, in height After warm treatment process, forerunner further reacts and recrystallizes, therefore crystallinity significantly improves.Other than the graphite peaks of carbon paper, It can also be observed that hexagonal crystal system Ni from figure3S2(JCPDS card number: 30-0863) and cubic system MnO (JSPDS card number: 06-0592) diffraction maximum.This illustrates that product is Ni3S2With the compound of MnO.For S2 sample, the spy of carbon paper can only be observed Peak is levied, illustrates Ni3S2With MnO carbon paper surface be not crystal form exist, for the material of deintercalation mechanism material crystalline difference Universal chemical property is poor, this is also consistent with subsequent electrochemical test result.S3 sample is due to passing through high-temperature calcination, crystallinity Also very good from the point of view of XRD test result, and there is Ni3S2Characteristic peak, but due in raw material be free of Mn element, observation Characteristic peak less than MnO.
Fig. 2 is the stereoscan photograph of three kinds of materials, in a figure it can be seen from it is complete compared to presoma S2 sample Cauliflower shape pattern (b figure), S1 sample basic pattern after calcining remains as cauliflower shape, and tight is outside carbon fiber Table.Illustrate that high-temperature process not will lead to Ni3S2The separation of/MnO and carbon fiber, combination between the two are relatively stable.But it is former This petal-like fold disappears, and becomes minimum spherical particle.This is because as the temperature rises, the object in script forerunner Matter further reacts and reunites, and fold ultimately becomes spherical little particle.What c figure indicated is electroplate liquid without Mn2+Obtained is pure Ni3S2Material (S3) sample.Different from compound, Ni3S2Pattern be 100-200nm nano flower, and its floriform appearance exists It is still maintained after calcining.And lower contrast, show that material is integrally relatively thin.This means that Ni3S2In the electrolytic solution and OH- Contact area it is bigger, the transmission path of ion and electronics is also narrower.And the nano flower-like Ni of carbon fibre growth3S2, but coat It is not fine and close enough.This shows its bad chemical property and low coulombic efficiency.
Fig. 3 is cauliflower pattern Ni made from embodiment 13S2/ MnO composite material (S1) and the presoma material without sintering Expect the element mapping graph of (S2) sample.It can clearly find out that Mn element and O element are uniformly distributed wherein from figure, but point Density it is relatively low, illustrate that MnO is distributed in presoma (S2) and finished product (S1), but content is not high.
Two, Ni3S2/ MnO composite material (S1) with without sintering persursor material (S2) and electroplate liquid be free of Mn2+Institute Pure Ni obtained3S2The comparative test of material (S3).
Respectively with above-mentioned cauliflower pattern Ni3S2/ MnO composite material (S1) and the persursor material (S2) without sintering with And electroplate liquid is free of Mn2+Obtained pure Ni3S2Material (S3) is working electrode, with three electrode test characterized systematically electrochemistries Energy.Since material is directly plated on collector carbon paper, the step of eliminating preparation work electrode.The group of three electrode test systems Dress is using silver silver chloride electrode as reference electrode, is to electrode with gauze platinum electrode, 1M KOH aqueous solution is electrolyte assembling.Electricity The cyclic voltammetry curve test in pond is tested on occasion China CHI760E electrochemical workstation, and charge-discharge test is in blue electricity It is carried out in Land CT-2001A test macro, voltage range is 0~0.6V (vs.Ag/AgCl).Fig. 4 is that embodiment 1 is made The cabbage pattern Ni obtained3S2The cyclic voltammetry of/MnO composite material (S1), charging and discharging curve, high rate performance and in 2A g-1 Cycle performance figure under current density.S1 material has a sharp reduction peak at 0.4V it can be seen from a figure, accordingly Oxidation peak is located at 0.47V, the polarizing voltage between two peaks only has 0.07V, it was demonstrated that the redox reaction has good Invertibity.Figure b also has more stable electrochemistry platform in corresponding current potential.It is smaller polarized the reason is that because be used as afflux The carbon paper of body provides the carbon fiber of bigger serface for Ni3S2/ MnO attachment, the resistance of good electric conductivity and not binder Hinder but also transmission efficiency of the electronics between collector and active material is higher.C figure has shown that S1 cycles samples stability is non- It is often outstanding, 2A g-1When initial specific capacities be 87.3mAh g-1, after the charge and discharge cycles that completion 450 is enclosed, specific capacity is still So it is maintained at 85.1mAh g-1, conservation rate is up to 97.5%.In the whole process, always close to 100%, this also says coulombic efficiency The redox reaction high reversible is illustrated.Battery is subjected to multiplying power test, 4A g under different current densities-1、8A g-1、 10A g-1、15A g-1The specific capacity of material is respectively 75mAh g under current density-1、60mAh g-1、50mAh g-1And 30mAh g-1；When electric current returns to 2A g-1Afterwards, specific capacity has also been restored to 83mAh g therewith-1, illustrate material under higher current density Remain to maintain the stabilization of structure and chemical property.Fig. 5 is persursor material (S2) cyclic voltammetry curve without sintering, charge and discharge Electric curve, high rate performance and in 2A g-1Cycle performance figure under current density.It can be seen from its cyclic voltammetry curve (a figure) Reduction peak is significantly smaller compared with oxidation peak, embodies poor coulombic efficiency, can also obtain from loop test and find out (c figure), library For human relations efficiency always in 60~100% fluctuations, this is very unfavorable for the stability of battery and safety.B figure can be seen that The reduction potential of S2 is declined slightly compared with S1, this is also to reduce for the output voltage of full battery, also results in full battery function The loss of rate density and energy density.Fig. 6 is electroplate liquid without Mn2+Obtained pure Ni3S2Material (S3) cyclic voltammetry curve, Charging and discharging curve, high rate performance and in 2A g-1Cycle performance figure under current density.It is compared in S2, coulombic efficiency is further It glides, although there is good initial capacity, can not maintain well, reduction potential also more declines, and shows to the greatest extent The content of pipe MnO is considerably less, but remains to Ni3S2Chemical property have tremendous increase.
Embodiment 2
With Ni described in embodiment 13S2The preparation method of/MnO composite material, the difference is that:
NiCl in mixed solution2Concentration be 2.5mmol L-1, MnCl2Concentration be 7.5mmol L-1, the concentration of thiocarbamide For 0.5mol L-1, electrodeposition time 30min, the high-temperature calcination time is 1 hour, obtains Ni3S2/ MnO composite material, carbon paper On active material quality be 1.5mg cm-2。
Graininess combination cauliflower shape is presented in the material morphology and densification is coated on carbon fiber surface, XRD test difference With carbon paper, Ni3S2With three kinds of different characteristic peaks of MnO, Mn element can be observed in element mapping.
Embodiment 3
With Ni described in embodiment 13S2The preparation method of/MnO composite material, the difference is that:
NiCl in mixed solution2Concentration be 15mmol L-1, MnCl2Concentration be 10mmol L-1, the concentration of thiocarbamide is 1mol L-1, electrodeposition time 120min, the high-temperature calcination time is 3 hours, obtains Ni3S2/ MnO composite material, on carbon paper Active material quality is 8mg cm-2。
Graininess combination cauliflower shape is presented in the material morphology and densification is coated on carbon fiber surface, XRD test difference With carbon paper, Ni3S2With three kinds of different characteristic peaks of MnO, Mn element can be observed in element mapping.
Embodiment 4
With Ni described in embodiment 13S2The preparation method of/MnO composite material, the difference is that:
NiCl in mixed solution2Concentration be 5mmol L-1, MnCl2Concentration be 10mmol L-1, the concentration of thiocarbamide is 0.5mol L-1, electrodeposition time 45min, the high-temperature calcination time is 1 hour, obtains Ni3S2/ MnO composite material, on carbon paper Active material quality be 3mg cm-2。
Graininess combination cauliflower shape is presented in the material morphology and densification is coated on carbon fiber surface, XRD test difference With carbon paper, Ni3S2With three kinds of different characteristic peaks of MnO, Mn element can be observed in element mapping.
Embodiment 5
With Ni described in embodiment 13S2The preparation method of/MnO composite material, the difference is that:
NiCl in mixed solution2Concentration be 10mmol L-1, MnCl2Concentration be 7.5mmol L-1, the concentration of thiocarbamide is 0.5mol L-1, electrodeposition time 100min, the high-temperature calcination time is 2 hours, obtains Ni3S2/ MnO composite material, on carbon paper Active material quality be 6mg cm-2。
Graininess combination cauliflower shape is presented in the material morphology and densification is coated on carbon fiber surface, XRD test difference With carbon paper, Ni3S2With three kinds of different characteristic peaks of MnO, Mn element can be observed in element mapping.

Claims (10)

1. a kind of Ni3S2/ MnO composite material, the Ni3S2/ MnO compound is that load has Ni on carbon paper3S2/ MnO active matter Matter, Ni3S2/ MnO active material shape is cauliflower shape, and active material loading is 1.5~8mgcm-2。
2. Ni according to claim 13S2/ MnO composite material, which is characterized in that active material loading is 4mgcm-2。
3. Ni described in claim 13S2The preparation method of/MnO composite material, comprises the following steps that
With NiCl2、MnCl2Mixed solution with thiocarbamide is electrolyte, by electro-deposition method, keeps carbon paper surface electro-deposition active Substance obtains forerunner's product, the then high-temperature calcination under inert atmosphere obtains Ni after washing is dry3S2/ MnO composite material.
4. Ni according to claim 33S2The preparation method of/MnO composite material, which is characterized in that in mixed solution NiCl2Concentration be 3~15mmol L-1, MnCl2Concentration be 2.5~10mmol L-1, the concentration of thiocarbamide is 0.25~1mol L-1；Preferably, NiCl in mixed solution2Concentration be 7.5mmol L-1, MnCl2Concentration be 5mmol L-1, the concentration of thiocarbamide For 0.5mol L-1。
5. Ni according to claim 33S2The preparation method of/MnO composite material, which is characterized in that electro-deposition voltage be- 0.8V~-0.9V constant voltage, electrodeposition time 30min-120min, during electro-deposition, carbon paper is work electricity Pole, gauze platinum electrode are to electrode, and calomel electrode is reference electrode.
6. Ni according to claim 53S2The preparation method of/MnO composite material, which is characterized in that electro-deposition voltage be- The constant voltage of 0.85V, electrodeposition time 60min.
7. Ni according to claim 33S2The preparation method of/MnO composite material, which is characterized in that the inert atmosphere For Ar gas, high-temperature calcination temperature is 350-550 DEG C, and calcination time is 1~3 hour；High-temperature calcination temperature is 400 DEG C, when calcining Between be 2 hours.
8. Ni according to claim 33S2The preparation method of/MnO composite material, which is characterized in that the carbon fiber of carbon paper is straight Diameter is 7-9 μm.
9. a kind of Ni3S2The preparation method of/MnO composite material, comprises the following steps that
With NiCl2、MnCl2Mixed solution with thiocarbamide is electrolyte, and it is heavy to carry out electricity to carbon paper under the constant potential of -0.85V Product obtains forerunner's product, then under Ar atmosphere, forges at 400 DEG C after keeping carbon paper surface electro-deposition active material, washing dry It burns 2 hours, obtains Ni3S2/ MnO composite material.
10. Ni described in claim 13S2The application of/MnO composite material is applied in water aqueous alkaline battery, as anode Materials'use.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110459745A (en) * 2019-08-11 2019-11-15 五邑大学 A kind of Ni3S2@VO2The preparation method of nanocomposite
CN114614030A (en) * 2022-03-30 2022-06-10 长沙理工大学 Transition metal sulfide modified electrode and preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201380A (en) * 2014-08-19 2014-12-10 北京科技大学 Preparation method of nano Ni3S2 material with lamellar structure

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104201380A (en) * 2014-08-19 2014-12-10 北京科技大学 Preparation method of nano Ni3S2 material with lamellar structure

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
ZEYING YAN等: "Cliff-like NiO/Ni3S2 Directly Grown on Ni Foam for Battery-type Electrode with High Area Capacity and Long Cycle Stability", 《ELECTROCHIMICA ACTA》 *
张润梅等: "Mn/NiO@Ni3S2复合材料的制备及性能研究", 《功能材料与器件学报》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110459745A (en) * 2019-08-11 2019-11-15 五邑大学 A kind of Ni3S2@VO2The preparation method of nanocomposite
CN114614030A (en) * 2022-03-30 2022-06-10 长沙理工大学 Transition metal sulfide modified electrode and preparation method and application thereof

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