CN110148723A - A kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material - Google Patents

A kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material Download PDF

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CN110148723A
CN110148723A CN201910415733.4A CN201910415733A CN110148723A CN 110148723 A CN110148723 A CN 110148723A CN 201910415733 A CN201910415733 A CN 201910415733A CN 110148723 A CN110148723 A CN 110148723A
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sns
nitrogen
doped carbon
carbon compound
ion battery
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曾令兴
刘俊彬
康碧玉
陈庆华
钱庆荣
黄宝铨
肖荔人
程涵
陈晓燕
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Fujian Normal University
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    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M10/054Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M10/058Construction or manufacture
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M4/362Composites
    • H01M4/366Composites as layered products
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01ELECTRIC 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
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • H01M4/625Carbon or graphite
    • 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
    • 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
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention discloses a kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material;The collagen protein powder extracted in the discarded ox-hide hair of the slave leather industry is waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source coating modification SnS2Graduation microballoon, can effectively improve the storage potassium performance of material.Technical solution is as follows: extracting from discarded ox hair and obtains collagen protein powder, tin source, sulphur source and collagen protein powder are successively added to ultrasound, magnetic agitation in dehydrated alcohol;Mixed solution is put into microwave reaction case and is reacted, 5%H is led in centrifuge washing drying2The calcining of/95%Ar gaseous mixture, which is made, has good storage potassium characteristic SnS2@nitrogen-doped carbon compound.The preparation process is simple, waste high-qualityization utilize, strong operability, raw material sources extensively and resources circulation, it is low in cost, can be mass-produced, meet environmental requirement.

Description

A kind of SnS with high performance2@nitrogen-doped carbon compound kalium ion battery negative electrode material Preparation method and application
Technical field
The invention belongs to kalium ion battery Material Field more particularly to a kind of SnS with high performance2@nitrogen-doped carbon is multiple Close the preparation method and application of object.
Background technique
In secondary energy sources storage system, lithium ion battery is received significant attention, and high speed development, we live in Locate visible (portable electronic products, communication apparatus, electric car etc.).However consider the finiteness of metal lithium resource, a large amount of lithiums Consumption made lithium resource increasingly deficient, only solely rely on lithium ion battery and be unable to satisfy the mankind to following need It asks.And have the metallic potassium of the same clan of similar physics and chemical property with lithium, reserves more horn of plenty, and energy storage mechnism is similar, because This kalium ion battery is most to be expected to replace one of the battery of lithium ion battery applications in we live.
However because potassium ion has the atomic radius bigger than lithium ion, existing major part lithium ion battery is negative The all unsuitable storage potassium of pole material, is primarily due to the problems such as interlamellar spacing is small, and dynamics is slow.Therefore finding has specific capacity It is high, can stable/embedding potassium electrode material have great importance.And artificial gold has special layer structure, has very high Storage potassium theoretical capacity (733 mAh g-1) and preferable storage potassium characteristic.However, artificial gold volume expansion when storing up potassium is huge, and Electric conductivity is poor, and conventional method of modifying is complex carbon material to improve its electric conductivity, and part inhibits its huge volume swollen It is swollen.The invention patent is using the collagen protein powder of discarded ox-hide hair preparation as structure inducer, nano-reactor and N doping Carbon source, to construct SnS2@nitrogen-doped carbon graduation microballoon, this can not only effectively slow down volume expansion bring material dusting, knot The problems such as structure collapses, and nitrogen atom doping can make the more active sites of material exposure, to improve the storage potassium performance of material.
The present invention by using discard the preparation of ox-hide hair collagen as structure inducer, nano-reactor and N doping Carbon source prepares SnS2@nitrogen-doped carbon compound.It is compared difference with conventional method and is: 1, N doping carbon source is from process hides The collagen that the discarded ox-hide hair of industry extracts, it is from a wealth of sources, and turn waste into wealth, more meet resources circulation as raw material With the strategy of Green Development;2, nitrogen-doped carbon can not only improve the structural stability and electric conductivity of material as substrate, moreover it is possible to sudden and violent Reveal more active sites, optimizes the storage potassium performance of material;3, collagen is fine by the collagen of chain as structure inducer Dimension complexing confinement tin source and sulphur source, induce SnS2It is grown to the graduation micro-sphere structure of two-dimensional ultrathin piece composition;4, pass through microwave Solvent-thermal method constructs SnS2@nitrogen-doped carbon composite material, method is simple, and preparation quickly, has the prospect of large-scale production;5, SnS2@nitrogen-doped carbon compound has special graduation micro-sphere structure, can effectively inhibit electrode material during storing up potassium Volume expansion;And the result shows that, which has excellent storage potassium performance, has application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of SnS with high performance2@nitrogen-doped carbon compound and preparation method thereof and Using, simple process, strong operability, the discarded ox-hide hair of raw material sources leather industry, waste higher value application is at low cost It is honest and clean, it can be mass-produced, meet environmental requirement.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of SnS with high performance2The preparation method of@nitrogen-doped carbon compound kalium ion battery negative electrode material, including it is as follows Step:
1) first discarded ox-hide hair is washed with deionized water, then 50-80 °C at a temperature of dry, then ground At fur powder;And be placed on fur powder in 30-50 °C of solder(ing)acid water-bath 1-2 hours, it is filtered, washed to neutrality, so It is dried at a temperature of 50-70 °C afterwards;Finally powder is added in ionic liquid, 90-120 °C at a temperature of stir strongly 1-3 hours, freeze-drying obtained collagen protein powder;
2) tin source, sulphur source and collagen protein powder for weighing certain mass are added in dehydrated alcohol, and elder generation is ultrasonic after a certain period of time, then Magnetic agitation 20-40 minutes;Mixed solution is put into 150-200 °C of microwave reaction case, and solvent heat 0.5-1 hours, centrifugation was washed It washs, black gray expandable powder is collected in 80 °C of drying;
3) black gray expandable powder obtained by step 2 is put into quartz boat, is 5%H in volume ratio2In/95%Ar atmosphere tube type furnace 350-650 °C calcining 2-4 hours, collect black solid sample, as SnS2@nitrogen-doped carbon compound.
Above-mentioned steps 1) in, the collagen protein powder is made using the discarded ox-hide hair of leather industry as raw material, work Skill is easy, is a kind of waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source coating modification SnS2Graduation microballoon;The ionic liquid is choline chloride and quality of glycol than the mixed solution for 1:2;The tin Source is that series contains pink salt, including is not limited to stannous chloride, stannic chloride, stannous sulfate;Tin source and collagen protein powder mass ratio For 1:0.5-1;In step 2, the tin source: sulphur source: the mass ratio of collagen protein powder is 4-8: 4-10: 3-5, collagen egg White powder: the mass volume ratio of dehydrated alcohol is 3-5 g:0.3-1 L.
SnS with high performance made from the above-mentioned preparation method of the present invention2@nitrogen-doped carbon compound kalium ion battery is negative Pole material is SnS2@nitrogen-doped carbon compound.
The SnS with high performance2@nitrogen-doped carbon compound kalium ion battery negative electrode material, it is characterised in that: SnS2@nitrogen-doped carbon compound has graduation micro-sphere structure;The collagen protein powder is waste higher value application product, And there is nitrogen-atoms abundant, can effectively improve the chemical property of material.
SnS with high performance made from the above-mentioned preparation method of the present invention2@nitrogen-doped carbon compound kalium ion battery is negative Pole material is SnS2The application of@nitrogen-doped carbon compound, it is characterised in that: the SnS2@nitrogen-doped carbon compound is applied to potassium In ion battery cathode, when voltage is 0.01-3.0 V, 1 A/g of high current density after charge and discharge cycles 100 times, specific capacity is steady 240 mAh/g or more are scheduled on, capacity retention ratio is up to 90% or more.
A kind of kalium ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: claim 1-2 SnS with high performance made from any preparation method2@nitrogen-doped carbon compound kalium ion battery negative electrode material: it leads The electric super P carbon of agent: it is equably coated in after binder CMC=80:10:10 mixed grinding on copper foil as working electrode, metallic potassium Piece is to electrode, the KPF of 1 mol/L6/ EC (ethylene carbonate), PC(propene carbonate) it is that electrolyte is assembled into 2025 types Button-type battery;All assemblings carry out in inert-atmosphere glove box.
Remarkable advantage of the invention is:
1) present invention used in collagen protein powder from leather industry discarded ox-hide hair, it is from a wealth of sources, belong to process hides work The waste higher value application of industry.Functioning as presoma nitrogen source, being doped in carbon material for collagen protein powder, can make material The more active sites of exposure, improve the storage potassium performance of material, to obtain SnS2@nitrogen-doped carbon compound.
2) nitrogen-doped carbon used in the present invention functions as carrier, plays to the artificial gold graduation microballoon auxiliary The electric conductivity of the buffer function, increase material that help and the infiltration for being conducive to electrolyte.On the one hand, nitrogen-doped carbon and artificial gold is slow It rushes system and provides certain free space for the volume expansion and contraction of artificial gold during de-/embedding potassium.On the other hand, nitrogen is mixed Miscellaneous carbon is conducive to the diffusion of electrolyte, electron conductivity is helped to improve, and can effectively fix artificial gold structure, into one Step improves it and stores up potassium performance.
3) present invention synthesizes SnS dexterously using the collagen of discarded ox-hide hair preparation as N doping carbon source2@nitrogen Adulterate carbon complex, the SnS that the embodiment of the present invention 1 obtains2@nitrogen-doped carbon compound is applied in kalium ion battery cathode, Voltage be 0.01-3.0 V, 1 A/g of high current density when charge and discharge cycles 100 times after, specific capacity stablize 240 mAh/g with On, capacity retention ratio is up to 90% or more.
4) SnS2@nitrogen-doped carbon compound is a kind of good kalium ion battery negative electrode material, and the present invention provides one kind Prepare SnS2The method of@nitrogen-doped carbon compound, the preparation process is simple, and equipment is easy to get, strong operability, and leather industry is given up Gurry higher value application, raw material sources are extensive and environmentally protective, low in cost, can mass production, meet environmental requirement.
Detailed description of the invention
Fig. 1 is the resulting SnS of embodiment 12The XRD diagram of@nitrogen-doped carbon compound.
Fig. 2 is the resulting SnS of embodiment 12The SEM of@nitrogen-doped carbon compound schemes.
Fig. 3 is the resulting SnS of embodiment 12In 50 mA/ when@nitrogen-doped carbon compound is as kalium ion battery negative electrode material Charging and discharging curve figure under g current density.
Fig. 4 is the resulting SnS of embodiment 12In 1 A/g when@nitrogen-doped carbon compound is as kalium ion battery negative electrode material Long-life cycle performance figure under current density.
Specific embodiment
Embodiment 1
1) first discarded ox-hide hair (the discarded ox-hide for referring to hairiness) is washed with deionized water, then at a temperature of 50 °C Drying, then it is milled to fur powder;And be placed on fur powder in 30 °C of solder(ing)acids water-bath 2 hours, it filters, wash It washs to neutrality, is then dried at a temperature of 50 °C;Powder is finally added to choline chloride and quality of glycol than for 1:2's In ionic liquid, 90 °C at a temperature of stir strongly 3 hours, freeze-drying obtain collagen protein powder;
2) 4 g stannous chlorides are weighed respectively, 6 g L-cysteines and 4 g collagen protein powders are added in 0.6 L dehydrated alcohol, First ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 150 °C of microwave reaction casees, and solvent heat 0.6 hour, Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, is 5%H in volume ratio2350 in/95%Ar atmosphere tube type furnace °C calcining 2 hours, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound kalium ion battery is negative Pole material --- SnS2@nitrogen-doped carbon compound;
The SnS for obtaining Fig. 1 is tested through XRD2The XRD diagram of@nitrogen-doped carbon compound, from fig. 1, it can be seen that the material that synthesis obtains is sulphur The standard diagram (JCPDS, 022-0951) of change tin, diffraction maximum position and artificial gold matches.It tests and obtains through scanning electron microscope The SnS of Fig. 22The SEM of@nitrogen-doped carbon compound schemes.The compound is graduation micro-sphere structure as shown in Figure 2, and surface is by piece The artificial gold of shape is formed;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1 The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings It is carried out in inert-atmosphere glove box.At 100 mA/g and 1 A/g current density, it is tested respectively and stores up potassium performance.Fig. 3 It is charging and discharging curve of the material under 50 mA/g current densities, as can be seen from the figure the electrode material is discharging it for the first time Afterwards, charging and discharging curve repeatability is preferable, illustrates it with good cyclical stability.As shown in Figure 4, SnS2@nitrogen-doped carbon is multiple When closing object as kalium ion battery negative electrode material, excellent storage potassium performance is shown, in the case where voltage is 0.01-3.0 V, in big electricity 100 specific capacities of charge and discharge cycles are stablized in 240 mAh/g when 1 A/g of current density, and capacity is unattenuated.Therefore, SnS2@N doping Carbon complex has good storage potassium performance, is environmentally friendly high-performance kalium ion battery negative electrode material, has good Application prospect.
Embodiment 2
1) first discarded ox-hide hair (the discarded ox-hide for referring to hairiness) is washed with deionized water, then at a temperature of 60 °C Drying, then it is milled to powder;And be placed on fur powder in 40 °C of solder(ing)acids water-bath 1.5 hours, it is filtered, washed To neutrality, then dried at a temperature of 50 °C;Finally by powder be added to choline chloride and quality of glycol than for 1:2 from In sub- liquid, 100 °C at a temperature of stir strongly 1 hour, freeze-drying obtain collagen protein powder;
2) 4 g stannic chlorides are weighed respectively, and 4 g L-cysteines and 3 g collagen protein powders are added in 0.3 L dehydrated alcohol, first Ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 170 °C of microwave reaction casees, and solvent heat 0.5 hour, from Heart washing, 80 °C of drying, collects black gray expandable powder;
3) it by black gray expandable powder obtained by step 1), is put into quartz boat, in 5%H2500 °C of calcinings in/95%Ar atmosphere tube type furnace 2 hours, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1 The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal It is carried out in inert-atmosphere glove box.
Embodiment 3
1) first discarded ox-hide hair (ox-hide for referring to hairiness) is washed with deionized water, then 70 °C at a temperature of dry, It is milled to powder again;And be placed on fur powder in 50 °C of solder(ing)acids water-bath 1 hour, it is filtered, washed to neutrality, Then it is dried at a temperature of 60 °C;Powder is finally added to choline chloride and quality of glycol than the ionic liquid for 1:2 In, 110 °C at a temperature of stir strongly 1 hour, freeze-drying obtain collagen protein powder;
2) 6 g stannous sulfates are weighed respectively, and 9 g L-cysteines and 5 g collagen protein powders are added in 1 L dehydrated alcohol, first Ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 190 °C of microwave reaction casees, and solvent heat 0.5 hour, Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, in 5%H2500 °C of calcinings 4 in/95%Ar atmosphere tube type furnace Hour, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1 The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal It is carried out in inert-atmosphere glove box.
Embodiment 4
1) first discarded ox-hide hair (ox-hide for referring to hairiness) is washed with deionized water, then 80 °C at a temperature of dry, It is milled to powder again;And be placed on fur powder in 50 °C of solder(ing)acids water-bath 1 hour, it is filtered, washed to neutrality, Then it is dried at a temperature of 70 °C;Powder is finally added to choline chloride and quality of glycol than the ionic liquid for 1:2 In, 120 °C at a temperature of stir strongly 2 hours, freeze-drying obtain collagen protein powder;
2) 8 g stannous chlorides are weighed respectively, and 4 g L-cysteines and 5 g collagen protein powders are added in 1 L dehydrated alcohol, first 10 min of ultrasound, then 30 min of magnetic agitation;Mixed solution is put into 200 °C of microwave reaction casees, and microwave solvothermal 0.5 hour, Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, in 5%H2600 °C of calcinings 4 in/95%Ar atmosphere tube type furnace Hour, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1 The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal It is carried out in inert-atmosphere glove box.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (6)

1. a kind of SnS with high performance2The preparation method of@nitrogen-doped carbon compound kalium ion battery negative electrode material, including it is as follows Step:
1) first discarded ox-hide hair is washed with deionized water, then 50-80 °C at a temperature of dry, then ground At fur powder;And be placed on fur powder in 30-50 °C of solder(ing)acid water-bath 1-2 hours, it is filtered, washed to neutrality, so It is dried at a temperature of 50-70 °C afterwards;Finally powder is added in ionic liquid, 90-120 °C at a temperature of stir strongly 1-3 hours, freeze-drying obtained collagen protein powder;
2) tin source, sulphur source and collagen protein powder for weighing certain mass are added in dehydrated alcohol, and elder generation is ultrasonic after a certain period of time, then Magnetic agitation 20-40 minutes;Mixed solution is put into 150-200 °C of microwave reaction case, and solvent heat 0.5-1 hours, centrifugation was washed It washs, black gray expandable powder is collected in 80 °C of drying;
3) black gray expandable powder obtained by step 2 is put into quartz boat, is 5%H in volume ratio2350- in/95%Ar atmosphere tube type furnace 650 °C calcining 2-4 hours, collect black solid sample, as SnS2@nitrogen-doped carbon compound.
2. SnS with high performance according to claim 12The system of@nitrogen-doped carbon compound kalium ion battery negative electrode material Preparation Method, it is characterised in that: in step 1), the collagen protein powder is using the discarded ox-hide hair of leather industry as raw material system , simple process is a kind of waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source cladding changes Property SnS2Graduation microballoon;The ionic liquid is choline chloride and quality of glycol than the mixed solution for 1:2;Described Tin source is that series contains pink salt, including is not limited to stannous chloride, stannic chloride, stannous sulfate;Tin source and collagen protein powder quality Than for 1:0.5-1;In step 2, the tin source: sulphur source: the mass ratio of collagen protein powder is 4-8: 4-10: 3-5, collagen Albumen powder: the mass volume ratio of dehydrated alcohol is 3-5 g:0.3-1 L.
3. SnS with high performance made from any preparation method of claim 1-22@nitrogen-doped carbon compound potassium ion Cell negative electrode material is SnS2@nitrogen-doped carbon compound.
4. SnS with high performance according to claim 32@nitrogen-doped carbon compound kalium ion battery negative electrode material, It is characterized in that: SnS2@nitrogen-doped carbon compound has graduation micro-sphere structure;The collagen protein powder is that waste is high-valued Using product, and there is nitrogen-atoms abundant, can effectively improve the chemical property of material.
5. SnS with high performance made from any preparation method of claim 1-22@nitrogen-doped carbon compound potassium ion Cell negative electrode material is SnS2The application of@nitrogen-doped carbon compound, it is characterised in that: the SnS2@nitrogen-doped carbon compound is answered For in kalium ion battery cathode, when voltage is 0.01-3.0 V, 1 A/g of high current density after charge and discharge cycles 100 times, than Capacity is stablized in 240 mAh/g or more, and capacity retention ratio is up to 90% or more.
6. a kind of kalium ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: claim 1-2 appoints SnS with high performance made from preparation method described in one2@nitrogen-doped carbon compound kalium ion battery negative electrode material: conductive The super P carbon of agent: it is equably coated in after binder CMC=80:10:10 mixed grinding on copper foil as working electrode, metallic potassium piece For to electrode, the KPF of 1 mol/L6/ EC (ethylene carbonate), PC(propene carbonate) it is that electrolyte is assembled into 2025 type knobs Button-type battery.
CN201910415733.4A 2019-05-18 2019-05-18 A kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material Pending CN110148723A (en)

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* Cited by examiner, † Cited by third party
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CN110931741A (en) * 2019-11-26 2020-03-27 上海大学 Tin sulfide quantum dot loaded titanium carbide composite nano material and preparation method thereof
CN111584845A (en) * 2020-05-20 2020-08-25 信阳师范学院 Preparation method and application of N, S co-doped carbon/tin disulfide composite material
CN112018358A (en) * 2020-08-17 2020-12-01 五邑大学 Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof
CN112038596A (en) * 2020-08-17 2020-12-04 嵊州市芝草科技有限公司 Mesoporous carbon coated SnS2The negative electrode material of the sodium ion battery and the preparation method thereof
CN112194173A (en) * 2020-09-30 2021-01-08 中南大学 Preparation method of tin sulfide/nitrogen doped flower-like carbon lithium ion battery cathode material and product thereof
WO2022021642A1 (en) * 2020-07-31 2022-02-03 广东凯金新能源科技股份有限公司 Sodium ion battery negative electrode material and preparation method therefor

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150372295A1 (en) * 2013-03-14 2015-12-24 Dic Corporation Metal tin-carbon composites, method for producing said composites, anode active material for non-aqueous lithium secondary batteries which is produced using said composites, anode for non-aqueous lithium secondary batteries which comprises said anode active material, and non-aqueous lithium secondary battery
CN105552366A (en) * 2015-12-17 2016-05-04 长沙理工大学 Preparation method of anode material, namely nitrogen-doped SnS/C composite nanomaterial for lithium battery
CN106887578A (en) * 2017-04-01 2017-06-23 中南大学 A kind of artificial gold/CNT composite Nano negative material and preparation method thereof
CN108598424A (en) * 2018-04-25 2018-09-28 新疆大学 A kind of SnS2Mesoporous carbon compound cathode materials of N doping and preparation method thereof
CN109286009A (en) * 2018-09-25 2019-01-29 陕西科技大学 A kind of preparation method of nanometer sheet self assembled three-dimensional nano flower artificial gold/graphitization carbonitride lithium ion battery negative material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150372295A1 (en) * 2013-03-14 2015-12-24 Dic Corporation Metal tin-carbon composites, method for producing said composites, anode active material for non-aqueous lithium secondary batteries which is produced using said composites, anode for non-aqueous lithium secondary batteries which comprises said anode active material, and non-aqueous lithium secondary battery
CN105552366A (en) * 2015-12-17 2016-05-04 长沙理工大学 Preparation method of anode material, namely nitrogen-doped SnS/C composite nanomaterial for lithium battery
CN106887578A (en) * 2017-04-01 2017-06-23 中南大学 A kind of artificial gold/CNT composite Nano negative material and preparation method thereof
CN108598424A (en) * 2018-04-25 2018-09-28 新疆大学 A kind of SnS2Mesoporous carbon compound cathode materials of N doping and preparation method thereof
CN109286009A (en) * 2018-09-25 2019-01-29 陕西科技大学 A kind of preparation method of nanometer sheet self assembled three-dimensional nano flower artificial gold/graphitization carbonitride lithium ion battery negative material

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
MEIYAZHAGAN ASHOKKUMAR等: "Transforming collagen wastes into doped nanocarbons for sustainable energy applications", 《GREEN CHEMISTRY》 *
王兆梅等: "胶原蛋白在离子液中的溶解及流变特性", 《MODERN FOOD SCIENCE AND TECHNOLOGY》 *
韩雪梅等: "皮革废弃物中胶原蛋白的提取研究进展", 《西部皮革》 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110931741A (en) * 2019-11-26 2020-03-27 上海大学 Tin sulfide quantum dot loaded titanium carbide composite nano material and preparation method thereof
CN111584845A (en) * 2020-05-20 2020-08-25 信阳师范学院 Preparation method and application of N, S co-doped carbon/tin disulfide composite material
CN111584845B (en) * 2020-05-20 2022-04-29 信阳师范学院 Preparation method and application of N, S co-doped carbon/tin disulfide composite material
WO2022021642A1 (en) * 2020-07-31 2022-02-03 广东凯金新能源科技股份有限公司 Sodium ion battery negative electrode material and preparation method therefor
CN112018358A (en) * 2020-08-17 2020-12-01 五邑大学 Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof
CN112038596A (en) * 2020-08-17 2020-12-04 嵊州市芝草科技有限公司 Mesoporous carbon coated SnS2The negative electrode material of the sodium ion battery and the preparation method thereof
CN112194173A (en) * 2020-09-30 2021-01-08 中南大学 Preparation method of tin sulfide/nitrogen doped flower-like carbon lithium ion battery cathode material and product thereof
CN112194173B (en) * 2020-09-30 2021-06-22 中南大学 Preparation method of tin sulfide/nitrogen doped flower-like carbon lithium ion battery cathode material and product thereof

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