CN104993131B - A kind of lithium ion battery negative material NiS/Ni and preparation method thereof - Google Patents

A kind of lithium ion battery negative material NiS/Ni and preparation method thereof Download PDF

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Publication number
CN104993131B
CN104993131B CN201510275254.9A CN201510275254A CN104993131B CN 104993131 B CN104993131 B CN 104993131B CN 201510275254 A CN201510275254 A CN 201510275254A CN 104993131 B CN104993131 B CN 104993131B
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nis
preparation
lithium ion
ion battery
negative material
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CN104993131A (en
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倪世兵
马建军
张继成
杨学林
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China Three Gorges University CTGU
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China Three Gorges University CTGU
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/581Chalcogenides or intercalation compounds thereof
    • H01M4/5815Sulfides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/64Carriers or collectors
    • H01M4/66Selection of materials
    • H01M4/661Metal or alloys, e.g. alloy coatings
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The present invention provides a kind of negative electrode of lithium ion battery, it is characterised in that the structure of the anode is NiS/Ni, and the preparation method of the anode is as follows:Take thiocarbamide to be placed in container, then add appropriate amount of deionized water and hydrogen peroxide to be sufficiently stirred, obtain homogeneous solution;Obtained homogeneous solution is transferred in hydrothermal reaction kettle liner, if taking dry plate nickel foam to be put into hydrothermal reaction kettle, at 90 ~ 150 DEG C react 4 ~ 10 it is small when after, natural cooling i.e. obtain NiS/Ni samples.Electrode preparation method is simple, and cost is low, and controllability is strong;Hydrothermal temperature is low, and the time is short;NiS homoepitaxials are made of, particle size is about 100 nm a large amount of particles in foam nickel surface in prepared NiS/Ni;Material prepared charge/discharge capacity is high, and cycle performance is excellent.

Description

A kind of lithium ion battery negative material NiS/Ni and preparation method thereof
Technical field:
The present invention relates to a kind of negative electrode of lithium ion battery, more particularly to a kind of preparation side of NiS/Ni negative electrode of lithium ion battery Method, belongs to field of electrochemical power source.
Technical background:
Lithium ion battery is because with the superior function such as high-energy-density, long circulation life, environmental-friendly, not only extensive use In portable electric appts, and continued to develop to the field such as power vehicle and energy-accumulating power station.High-performance lithium ion electricity Development of the development in pond for future electronic product, power vehicle and energy-accumulating power station is with very important meaning.
At present, positive electrode is mainly the transition group metallic oxide containing lithium, their theoretical lithium storage content is relatively low, existing There is the capacity possibility for increasing substantially them on the basis of cathode material structure little, further improve the capacity of lithium ion battery Rely only on the raising of negative material capacity.At present, commercial li-ion battery cathode is mainly graphite-like carbon material.But it is managed It is relatively low by capacity(372 mAh/g), it has been difficult to meet the needs of energy-storage battery, and the battery brought is separated out there are dendrite lithium The short circuit even safety problem such as explosion.New, high performance lithium ionic cell cathode material is researched and developed for high performance lithium ion battery Development have great importance.In all kinds of negative materials, conversion hysteria negative material is higher with theoretical capacity(500~1000 mAh/g), synthetic method is simple, the advantages such as material manufacturing cost is low, becomes the novel anode material of a kind of great potential.Turn Main problem existing for material of remodeling is:Material conductivity is poor, and meeting material morphology can occur with structure in cyclic process Destroy, cause chemical property undesirable.By the way that conversion hysteria material in situ is grown on conducting base, can not only significantly carry The electric conductivity of high material, at the same can effective pattern and structural stability of the reinforcing material in cyclic process, so as to greatly promote Its chemical property.In addition, material of the growth in situ on conducting base can be directly used as negative electrode of lithium ion battery, it is not required to make With any binding agent and technology for preparing electrode, electrode preparation efficiency can be effectively improved, is had in lithium ion battery important Application value.
NiS is a kind of new conversion hysteria negative material, has important application value in lithium ion battery.However, close Carry out less in the preparation of NiS/Ni composite constructions and its application study in lithium ion battery.We pass through low temperature early period It is dry pre-sulfiding to be prepared for NiS/Ni composite constructions, preferable chemical property is shown using it as negative electrode of lithium ion battery.But It is that dry method is it is difficult to ensure that NiS in Ni surfaces homoepitaxial, and easily S residuals occurs(J. Mater. Chem., 2012, 22, 2395-2397).It is expected to realize uniform, the growth in situ of nickel foam surface sulfide thing by wet heating.However, due to Ni higher Thermodynamic stability, usually under thermal and hydric environment, it is difficult to sulphur source react and obtain NiS.Based on background above, this patent hair A kind of bright hydro-thermal method prepares NiS/Ni composite constructions, and higher specific capacity and excellent is shown using it as negative electrode of lithium ion battery Cyclical stability, correlative study has no report.
Goal of the invention
The purpose of the present invention is exactly using thiocarbamide, nickel foam as reaction raw materials, using hydrogen peroxide as reaction promoter, passes through hydro-thermal Reaction prepares binder free NiS/Ni negative electrode of lithium ion battery.
Raw material prepared by NiS/Ni composite materials according to the present invention are thiocarbamide, hydrogen peroxide, nickel foam, thiocarbamide, double Oxygen water, the mass ratio of nickel foam are 1 ~ 10:2~4:100~200.In material preparation process, take thiocarbamide to be placed in container, add appropriate Hydrogen peroxide and deionized water stir evenly, the solution stirred evenly is transferred in hydrothermal reaction kettle, then in hydro-thermal reaction If being put into the foam nickel sheet of dry plate certain size in kettle, when reaction 4 ~ 10 is small under the conditions of 90 ~ 150 DEG C, natural cooling obtains NiS/Ni samples.
NiS/Ni anode involved in the present invention and preparation method have following distinguishing feature:
(1)Electrode preparation method is simple, and cost is low, and controllability is strong;
(2)Hydrothermal temperature is low, and the time is short;
(3)NiS homoepitaxials are made of, particle size is about a large amount of particles in foam nickel surface in prepared NiS/Ni 100 nm;
(4)Prepared NiS/Ni can be directly used as negative electrode of lithium ion battery, without binding agent, eliminate conventional electrodes system The scraped finish of standby technique and etc..
Brief description of the drawings
The XRD spectrum of sample prepared by Fig. 1 embodiments 1;
The SEM spectrum of sample prepared by Fig. 2 embodiments 1;
(a) of sample prepared by Fig. 3 embodiments 1 charge and discharge curve and (b) cycle performance figure first;
(a) of sample prepared by Fig. 4 embodiments 2 charge and discharge curve and (b) cycle performance figure first;
(a) of sample prepared by Fig. 5 embodiments 3 charge and discharge curve and (b) cycle performance figure first.
Embodiment
Embodiment 1
Raw material is 5 by thiocarbamide, hydrogen peroxide, nickel foam mass ratio in NiS/Ni composite materials:3:150 carry out dispensing;Weigh Thiocarbamide is placed in beaker, adds suitable hydrogen peroxide and deionized water to stir evenly, and it is anti-that the solution stirred evenly is transferred to hydro-thermal Answer in kettle, if then adding the foam nickel sheet of dry plate certain size in hydrothermal reaction kettle, when reaction 5 is small under the conditions of 120 DEG C, Natural cooling obtains NiS/Ni samples.By prepared NiS/Ni deionized water rinsings, and dried in 60 DEG C of baking ovens.Institute The sample of preparation is through XRD diagram spectrum analysis, such as Fig. 1 peak positions and NiS (XRD cards JCPDS, No. 01-1286) and Ni(04- 0850)It is corresponding.Prepared sample is characterized through SEM, as seen from Figure 2, in sample NiS homoepitaxials in foam nickel surface, It is made of a large amount of particles, particle size is about 100 nm.Button cell is made in 1 gained NiS/Ni of embodiment as follows: Obtained NiS/Ni samples are cut into the electrode slice of a diameter of 14 mm, 12h is dried in vacuo at 120 DEG C.Using metal lithium sheet as To electrode, Celgard films are membrane, dissolved with LiPF6EC+DMC+DEC (the volume ratios 1 of (1mol/L):1:1) solution For electrolyte, CR2025 type batteries are assembled into the glove box of argon gas protection.Battery pack stands 8h after installing, then uses CT2001A battery test systems carry out constant current charge-discharge test, and test voltage is 3 ~ 0.02V.Fig. 3 shows, prepared by embodiment 1 NiS/Ni electrodes charge and discharge capacity is respectively 862 and 1097 mAh/g first, charge and discharge capacity is after 50 circulations 630 and 647 mAh/g, it is shown that higher specific capacity and excellent stable circulation performance.
Embodiment 2
Raw material is 1 by thiocarbamide, hydrogen peroxide, nickel foam mass ratio in NiS/Ni composite materials:4:180 carry out dispensing;Weigh Thiocarbamide is placed in beaker, adds suitable hydrogen peroxide and deionized water to stir evenly, and it is anti-that the solution stirred evenly is transferred to hydro-thermal Answer in kettle, the foam nickel sheet of some certain sizes is then added in hydrothermal reaction kettle, when reaction 5 is small under the conditions of 90 DEG C, from So cooling obtains NiS/Ni samples.By prepared NiS/Ni deionized water rinsings, and dried in 60 DEG C of baking ovens.With institute The NiS/Ni of preparation is anode, is prepared into button cell by step in embodiment 1 and its chemical property is analyzed.Such as figure Shown in 4, charge and discharge capacity is respectively 741 and 923 mAh/g to the NiS/Ni anode prepared by embodiment 2 first, circulates it 50 times Charge and discharge capacity is respectively 576 and 594 mAh/g afterwards.
Embodiment 3
Raw material is 9.5 by thiocarbamide, hydrogen peroxide, nickel foam mass ratio in NiS/Ni composite materials:2.4:118 carry out dispensing; Weigh thiocarbamide to be placed in beaker, add suitable hydrogen peroxide and deionized water to stir evenly, the solution stirred evenly is transferred to water In thermal response kettle, the foam nickel sheet of some certain sizes is then added in hydrothermal reaction kettle, it is small that 5 are reacted under the conditions of 150 DEG C When natural cooling obtain NiS/Ni samples.By prepared NiS/Ni deionized water rinsings, and dried in 60 DEG C of baking ovens. Using prepared NiS/Ni as anode, it is prepared into button cell by step in embodiment 1 and its chemical property is analyzed. As shown in figure 5, as negative electrode of lithium ion battery, charge and discharge capacity is respectively 651 Hes to the NiS/Ni prepared by embodiment 3 first 817 mAh/g, charge and discharge capacity is respectively 485 and 512 mAh/g after 50 circulations.

Claims (1)

1. a kind of preparation method of lithium ion battery negative material, it is characterised in that the chemical composition of the negative material is NiS/ Ni, the preparation method of the negative material are as follows:
(1)Take thiocarbamide to be placed in container, then add appropriate amount of deionized water and hydrogen peroxide to be sufficiently stirred, obtain homogeneous solution;
(2)By step(1)Obtained homogeneous solution is transferred in hydrothermal reaction kettle liner, if it is anti-to take dry plate nickel foam to be put into hydro-thermal Answer kettle, at 120 DEG C react 5 it is small when after, natural cooling i.e. obtain NiS/Ni samples, thiocarbamide, hydrogen peroxide, the mass ratio of nickel foam For 5:3:Charge and discharge capacity is respectively 862mAh/g and 1097mAh/g to 150, NiS/Ni electrodes first, filled after 50 circulations, Discharge capacity is respectively 630 mAh/g and 647 mAh/g.
CN201510275254.9A 2015-05-27 2015-05-27 A kind of lithium ion battery negative material NiS/Ni and preparation method thereof Active CN104993131B (en)

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CN106207098A (en) * 2016-09-14 2016-12-07 三峡大学 A kind of preparation method of binder free NiO/Ni sodium-ion battery negative pole
CN106960957A (en) * 2017-04-24 2017-07-18 三峡大学 A kind of binder free compound N iS/Ni sodium-ion batteries negative pole and preparation method
CN109187698B (en) * 2018-08-09 2021-02-09 杭州电子科技大学 Hydrogen peroxide electrochemical sensor based on nickel sulfide nanoenzyme
CN109686591B (en) * 2018-12-17 2020-09-11 东南大学 Flake Ni3S2Cladding columnar Ni3S2Preparation method of array electrode

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CN102324321B (en) * 2011-08-26 2012-11-28 吉林大学 Metallic nickel oxide/carbon composite electrode material carried by nickel foam substrate
CN103915649A (en) * 2014-04-22 2014-07-09 合肥工业大学 High-energy-density lithium ion battery and preparation method thereof
CN104201380B (en) * 2014-08-19 2017-02-15 北京科技大学 Preparation method of nano Ni3S2 material with lamellar structure

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