CN110265637A - A kind of synthetic method and application of the derivative porous carbon complex anode material of lithium-ion battery of the tungsten selenide of excellent properties-collagen - Google Patents

A kind of synthetic method and application of the derivative porous carbon complex anode material of lithium-ion battery of the tungsten selenide of excellent properties-collagen Download PDF

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CN110265637A
CN110265637A CN201910415732.XA CN201910415732A CN110265637A CN 110265637 A CN110265637 A CN 110265637A CN 201910415732 A CN201910415732 A CN 201910415732A CN 110265637 A CN110265637 A CN 110265637A
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collagen
porous carbon
tungsten
tungsten selenide
ion battery
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CN110265637B (en
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陈庆华
康碧玉
曾令兴
钱庆荣
黄宝铨
肖荔人
罗奋强
方益兴
庄凌峰
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Fujian Normal 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 discloses the synthetic method and application of a kind of derivative porous carbon complex anode material of lithium-ion battery of tungsten selenide-collagen of excellent properties, and the tungsten selenide particle confinement in the material is in porous nano carbon, stable structure；There is N and S hetero atom codope in porous carbon derived from the collagen, electric conductivity, and effectively fixed tungsten selenide particle can be improved by adjusting derived carbon internal electronic architecture, make stable structure, store up sodium performance to improve it.Technical solution is as follows: extracting collagen protein powder from the discarded ox-hide hair of leather industry first, after its carbonization-activation and tungsten source is compound, and the derivative porous carbon complex of tungsten selenide-collagen is made in last selenizing.The result shows that the anode material of lithium-ion battery has excellent chemical property.The synthesis technology is simple, strong operability, while the waste green higher value application of leather industry, agrees with national resources circulation Strategic Demand, low in cost, can be mass-produced, meets environmental requirement.

Description

A kind of derivative porous carbon complex sodium ion of the tungsten selenide of excellent properties-collagen The synthetic method and application of cell negative electrode material
Technical field
The invention belongs to tungsten selenide-collagens of sodium-ion battery Material Field more particularly to a kind of excellent properties to spread out The synthetic method and application of raw porous carbon complex.
Background technique
Lithium ion battery (LIBs) has many advantages, such as high-energy and high power density, is widely used to portable electronic and sets Standby and electric car etc..However, lithium resource is rare, it is unevenly distributed, and at high cost, largely constrains and answer on a large scale Development.Meanwhile the safety problem of lithium battery is always a great problem of field of lithium.So as alternative energy source, tool Have the advantages that low cost, high-performance, high security energy storage device sodium-ion battery come into being.However, due to Na+Radius ratio Li+Radius is big, leads to the development Challenge of sodium-ion battery, such as large volume expansion, dynamic performance difference.Therefore, if Counting, there is the anode material of lithium-ion battery of excellent properties to have great importance.
And two-dimensional layer transition metal such as MoS in recent years2、MoSe2Deng due to the two-dimensional layered structure with class graphene and There is biggish interlamellar spacing, is conducive to the Na of relatively large radius+Transimission and storage, while they have good electric conductivity, performance More excellent chemical property out.Although WSe2With physicochemical properties identical with them, but its density is opposite It is heavier, MoS is compared on theoretical specific discharge capacity2、MoSe2It is low.However, WSe2Overpotential it is lower, and WSe2Density it is bigger because This volume and capacity ratio is higher, has in fields such as power battery, submarine battery and the aeronautical cells that volumetric spaces are limited good Application prospect is the potential next-generation sodium ion negative electrode material of tool.
The present invention is synthesized using the collagen protein powder extracted from the discarded ox-hide hair of leather industry as presoma carbon source The derivative porous carbon complex of tungsten selenide-collagen.It is compared difference with conventional method and is: 1, porous derived from collagen Nano Carbon object has high voidage, the features such as high-specific surface area, it is possible to provide a large amount of storage sodium active site, be conducive to sodium from The transmission of son and electronics, while promoting electrolyte permeability to the inside of active material, promote kinetics；2, collagen is It is extracted from discarded ox-hide hair, belongs to the waste green higher value application of leather industry, turn waste into wealth, advantageously reduce Environmental pollution；3, the collagen discarded in ox-hide hair is a kind of natural high molecular material, is made of, is rich in a variety of amino acid Organic group, a large amount of N in collagen, S element can be converted in situ into N in calcination process, and S Heteroatom doping is adjustable The electronic structure inside derived carbon is controlled, the electric conductivity of compound is improved, and can effectively reinforce the combination of derived carbon and tungsten selenide, makes Structure is more stable, and then improves its chemical property；4, porous nano carbon derived from collagen is by tungsten selenide particle confinement In porous structure, make stable structure, the volume change in charge and discharge process can be buffered；5, more by collagen activation derivative Hole carbon and a step selenizing method synthetic material, simple process, strong operability turn waste into wealth simultaneously, and high level conversion is low in cost, Prospect with large-scale production.And the result shows that, which has excellent chemical property, has Certain application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of derivative porous carbon complex of tungsten selenide haveing excellent performance-collagen and its Synthetic method and application, simple process, strong operability, the waste higher value application of leather industry is low in cost, can advise greatly Mould production, meets environmental requirement.
To achieve the above object, the present invention adopts the following technical scheme:
The present invention synthesizes the derivative porous carbon complex of tungsten selenide-collagen using simple and easy activation and selenizing method.Its Specific step is as follows:
1) the discarded ox-hide hair (ox-hide for referring to hairiness) of certain mass is weighed, first ultrasound pretreatment in ethanol, then is cut with scissors It is broken, the enzyme preparation dissolution for accounting for material quality 0.5% -1% is added, the enzyme preparation uses pepsin/papain/pancreas Protease is then saltoutd, and finally freeze-drying grinds to obtain collagen protein powder.
2) collagen protein powder and zinc chloride are weighed in polytetrafluoroethyllining lining according to mass ratio 1:(0.2-2), are added suitable The water of amount stirs 4-8 h, in N after drying21- is activated in 500-900 oC with heating rate 5-10 oC/min in atmosphere tube type furnace 2 h, after washing and drying, collect black solid sample；
3) the resulting sample of the step of weighing certain mass (2) and tungsten add a certain amount of distilled water in beaker, acutely 6-12 h is stirred, solid sample is finally collected in centrifugation drying；
4) by black sample grind into powder obtained by step 3) and be 1:(1.5-3 with mass ratio with Se powder) be individually positioned in two In corundum boat, in 10% vol H2It calcines 2-5 hours in/90 vol %Ar atmosphere tube type furnaces in 500-800 oC, finally collects Black powder sample derives porous carbon complex to get to tungsten selenide-collagen；
In step 2, the collagen is to extract to obtain from the discarded ox-hide hair of leather industry, rich in have Machine group and amino acid, can activate into N, the porous carbon of S codope, and by tungsten selenide nanoparticle confinement in porous structure； The tungsten source can be serial tungsten salt, including be not limited to sodium tungstate, tungsten chloride, phosphotungstic acid；Sample after the activation Product and the mass ratio in tungsten source are 1:2-5, and the mixing time is 6-12 h, and drying temperature is 80-100 °C；In step 4), The mass ratio of black sample obtained by the step 3) and selenium powder is 1:1.5-3, and calcination temperature is 500-800 °C, and calcination time is 2-5 hours.
Composite carbon in the derivative porous carbon complex of the tungsten selenide-collagen is the porous nano of nitrogen sulphur codope Carbon has high porosity and high-specific surface area, is conducive to store up sodium.The derivative porous carbon complex of the tungsten selenide-collagen Applied in sodium-ion battery cathode, charge and discharge cycles 50 times when voltage is 0.01-3.0 V, current density is 100 mA/g, Specific capacity is up to 368.2 mAh/g, and in 1 A/g of high current density after charge and discharge cycles 500 times, specific capacity is remained at 185.5 mAh/g, coulombic efficiency with higher, while also there is excellent high rate performance.
A kind of sodium-ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: above-mentioned synthesis The derivative porous carbon complex of tungsten selenide made from method-collagen: conductive agent acetylene black: binder CMC=80: 10: It is equably coated in after 10 mixed grindings on copper foil as working electrode, metallic sodium piece is to electrode, the NaPF of 1 mol/L6/ carbon Vinyl acetate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into 2032 type button-type batteries.Above-mentioned tungsten selenide-collagen The application that protein derived porous carbon answers object is to bear the derivative porous carbon complex of tungsten selenide-collagen applied to sodium-ion battery In extremely.Sodium-ion battery assembling: being in mass ratio the derivative porous carbon complex of tungsten selenide-collagen: conductive agent acetylene black: viscous Work electrode be equably coated on copper foil after knot CMC=80: 10: 10 mixed grinding of agent, and metallic sodium piece is to electrode 1 The NaPF of mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into button cell；All groups Dress carries out in inert-atmosphere glove box.
Remarkable advantage of the invention is:
1) collagen protein powder that the present invention is extracted from the discarded ox-hide hair of leather industry activates the porous of derivative nitrogen sulphur codope For nano-sized carbon as carrier, one side porous nanometer structure is conducive to the transmission of sodium ion/electronics and the infiltration of electrolyte, improves anti- Dynamics, the internal electronic architecture of its controllable derived carbon of another aspect nitrogen sulphur codope are answered, and then improves the conduction of compound Property.
2) collagen is extracted from the discarded ox-hide hair of leather industry, belongs to the waste high level of leather industry Change and utilize, turn waste into wealth, advantageously reduce environmental pollution, is used as presoma carbon source, it is low in cost.
3) confinement of tungsten selenide nanoparticle can be effectively suppressed tungsten selenide and generate reunion in porous structure, while structure is steady It is fixed, certain cushion space is provided for the volume expansion in charge and discharge process.
4) the derivative porous carbon complex of tungsten selenide of the invention-collagen is a kind of completely new sodium-ion battery cathode, The derivative porous carbon complex of the tungsten selenide that the embodiment of the present invention 1 obtains-collagen is applied in sodium-ion battery cathode, in electricity Charge and discharge cycles 50 times when pressure is 0.01-3.0 V, current density is 100 mA/g, specific capacity is up to 368.2 mAh/g, big When 1 A/g of current density after charge and discharge cycles 500 times, specific capacity remains at 185.5 mAh/g, coulomb effect with higher Rate, while also there is excellent high rate performance.
5) the derivative porous carbon complex of tungsten selenide-collagen is a kind of excellent anode material of lithium-ion battery, this hair Bright to provide a kind of method of derivative porous carbon complex of synthesis tungsten selenide-collagen for the first time, the preparation process is simple, can grasp The property made is strong, the waste higher value application of leather industry, low in cost, can mass production, meet environmental requirement.
Detailed description of the invention
Fig. 1 is the XRD diagram of the derivative porous carbon complex of the resulting tungsten selenide of embodiment 1-collagen.
Fig. 2 is the derivative porous carbon complex of the resulting tungsten selenide of embodiment 1-collagen as sodium-ion battery cathode material Cycle performance curve graph when material under 100 mA/g current densities.
Fig. 3 is the derivative porous carbon complex of the resulting tungsten selenide of embodiment 1-collagen as sodium-ion battery cathode material Charging and discharging curve figure when material under 100 mA/g current densities.
Fig. 4 is the derivative porous carbon complex of the resulting tungsten selenide of embodiment 1-collagen as sodium-ion battery cathode material Long-life cycle performance figure and coulombic efficiency figure when material under 1 A/g current density.
Fig. 5 is the derivative porous carbon complex of the resulting tungsten selenide of embodiment 1-collagen as sodium-ion battery cathode material High rate performance figure when material under different current densities.
Specific embodiment
Embodiment 1
1) the discarded ox-hide hair (the discarded ox-hide for referring to hairiness) of certain mass is weighed, first ultrasound pretreatment in ethanol, then with cutting Knife shreds, and the pepsin dissolution for accounting for material quality 0.5% is added, then saltouts, finally freeze-drying grinds to obtain collagen egg White powder.
2) 1g collagen protein powder and 1g zinc chloride are weighed respectively into polytetrafluoroethyllining lining, and suitable water stirring 4 is added H, in N after drying2It is collected black after 600 oC, 1 h of activation, washing and drying in atmosphere tube type furnace with the heating rate of 5 oC/min Color solid sample；
3) 1:2 in mass ratio weighs the resulting sample of step 2 and phosphotungstic acid adds a certain amount of distilled water in beaker, acute 6 h of strong stirring, centrifugation drying, finally collect solid sample；
4) two have been individually positioned in just for 1:1.5 with mass ratio by step 3) obtained solid sample grind into powder and with Se powder Yu Zhouzhong, in 10% vol H2It is calcined 4 hours in/90 vol %Ar atmosphere tube type furnaces in 500 oC, finally collects black powder Sample derives porous carbon complex sodium-ion battery cathode material to get to the tungsten selenide with excellent properties-collagen The derivative porous carbon complex of material --- tungsten selenide-collagen；
The X ray diffracting spectrum for obtaining the derivative carbon complex of tungsten selenide-collagen of Fig. 1, as seen from the figure, 2 θ are tested through XRD Correspond to (002) crystal face of the derivative porous carbon of collagen for 26.0 ° of diffraction maximums, and 2 θ are 13.7 °, 31.4 °, 37.9 °, 56.0 °, there is wider diffraction maximum and respectively corresponds WSe in 69.6 ° of position2(JCPDS:71-0600) (002) in, (100), (103), (110) and (203) crystal face illustrates that synthesized tungsten selenide is nanostructure, has lesser partial size. Using the derivative porous carbon complex of tungsten selenide-collagen of the present embodiment synthesis: conductive agent acetylene black: binder CMC according to It is equably coated in after 80: 10: 10 mixed grinding of mass percent on copper foil as working electrode, metallic sodium piece is to electricity Pole, the NaPF of 1 mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into button cell； All assemblings carry out in inert-atmosphere glove box.Under 100 mA/g current densities, test loop performance as shown in Fig. 2, It is 0.01-3.0 V, electricity in voltage when the derivative porous carbon complex of tungsten selenide-collagen is as anode material of lithium-ion battery 50 specific capacities of charge and discharge cycles are up to 368.2 mAh/g when current density is 100 mA/g.Fig. 3 is the material in 100 mA/g electricity Charging and discharging curve under current density, as can be seen from the figure after recycling for the first time, charging and discharging curve weighs the electrode material substantially It is combined, illustrates its electrochemical stability with higher in charge and discharge process.Fig. 4 is under 1 A/g current density Long-life cycle performance figure and coulombic efficiency figure, as seen from the figure, even if electrode material charge and discharge in 1 A/g of high current density After circulation 500 times, the specific capacity of 185.5 mAh/g is remained at, illustrates that the material has stable long-life cycle performance.Separately Outside, the corresponding coulombic efficiency curve of right axis of ordinates can obtain from figure, and after the circle of circulation 10, coulombic efficiency is stable always to be connect Nearly 100% or so, electrode material discharge capacity almost without decaying, illustrate the compound features go out good coulombic efficiency and Stable cycle performance.It is 0.01-3.0 V that Fig. 5, which is in voltage, and the high rate performance figure under different current densities as seen from the figure should Electrode is in 0.05 A/g, 0.1 A/g, 0.2 A/g, 0.5 A/g, 1 A/g, the specific capacity under the current density of 2 A/g point It Wei not 392.9 mAh/g, 378.1 mAh/g, 330.8 mAh/g, 289.9 mAh/g, 253.7 mAh/g, 219.2 MAh/g, and specific capacity stills remain in 370 mAh/g after electric current returns to 0.1 A/g, 100 circle of circulation, illustrates be circulated throughout The derivative porous carbon complex of tungsten selenide in journey-collagen keeps preferable pattern and structure, material collapse there is no occurring and Dusting, therefore there is excellent high rate performance.
Therefore, the derivative porous carbon complex of tungsten selenide-collagen not only has height ratio capacity under low current density, There is stable cycle performance under high current density, and there is excellent high rate performance, be environmentally friendly high-performance sodium Ion battery cathode material has a good application prospect.
Embodiment 2
1) the discarded ox-hide hair (the discarded ox-hide for referring to hairiness) of certain mass is weighed, first ultrasound pretreatment in ethanol, then with cutting Knife shreds, and the papain dissolution for accounting for material quality 0.8% is added, then saltouts, finally freeze-drying grinds to obtain collagen Albumen powder.
2) 2 g collagen protein powders and 4 g zinc chloride are weighed respectively into polytetrafluoroethyllining lining, and suitable water stirring is added 8 h, in N after drying2It is received after 700 oC, 2 h of activation, washing and drying in atmosphere tube type furnace with the heating rate of 10 oC/min Collect black solid sample；
3) 1:3 in mass ratio weighs the resulting sample of step 2 and sodium tungstate adds a certain amount of distilled water in beaker, acute 8 h of strong stirring, centrifugation drying, finally collect solid sample；
4) two corundum are individually positioned in for 1:2 with mass ratio by black sample grind into powder obtained by step 3) and with Se powder In boat, in 10% vol H2It is calcined 3 hours in/90 vol %Ar atmosphere tube type furnaces in 600 oC, finally collects black powder sample Product derive porous carbon complex to get to tungsten selenide-collagen；
Using the derivative porous carbon complex of tungsten selenide-collagen of the present embodiment synthesis: conductive agent acetylene black: binder CMC According to electrode of working equably is coated on copper foil after 80: 10: 10 mixed grinding of mass percent, metallic sodium piece is pair Electrode, the NaPF of 1 mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into button electricity Pond；All assemblings carry out in inert-atmosphere glove box.
Embodiment 3
1) the discarded ox-hide hair (ox-hide for referring to hairiness) of certain mass is weighed, first ultrasound pretreatment in ethanol, then is cut with scissors It is broken, the trypsase dissolution for accounting for material quality 0.7% is added, then saltouts, finally freeze-drying grinds to obtain collagen protein powder.
2) 2 g collagen protein powders and 0.5 g zinc chloride are weighed respectively into polytetrafluoroethyllining lining, and suitable water is added and stirs 6 h are mixed, in N after drying2It is received after 800 oC, 1 h of activation, washing and drying in atmosphere tube type furnace with the heating rate of 5 oC/min Collect black solid sample；
3) 1:4 in mass ratio weighs the resulting sample of step 2 and tungsten chloride adds a certain amount of distilled water in beaker, acute 10 h of strong stirring, centrifugation drying, finally collect solid sample；
4) two corundum are individually positioned in for 1:3 with mass ratio by black sample grind into powder obtained by step 3) and with Se powder In boat, in 10% vol H2It is calcined 2 hours in/90 vol %Ar atmosphere tube type furnaces in 700 oC, finally collects black powder sample Product derive porous carbon complex to get to tungsten selenide-collagen；
Using the derivative porous carbon complex of tungsten selenide-collagen of the present embodiment synthesis: conductive agent acetylene black: binder CMC According to electrode of working equably is coated on copper foil after 80: 10: 10 mixed grinding of mass percent, metallic sodium piece is pair Electrode, the NaPF of 1 mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into button electricity Pond；All assemblings carry out in inert-atmosphere glove box.
Embodiment 4
1) the discarded ox-hide hair (ox-hide for referring to hairiness) of certain mass is weighed, first ultrasound pretreatment in ethanol, then is cut with scissors It is broken, the pepsin dissolution for accounting for material quality 1% is added, then saltouts, finally freeze-drying grinds to obtain collagen protein powder.
2) 3 g collagen protein powders and 2 g zinc chloride are weighed respectively into polytetrafluoroethyllining lining, and suitable water stirring is added 8 h, in N after drying2It is received after 900 oC, 2 h of activation, washing and drying in atmosphere tube type furnace with the heating rate of 10 oC/min Collect black solid sample；
3) 1:3 in mass ratio weighs the resulting sample of step 2 and phosphotungstic acid adds a certain amount of distilled water in beaker, acute 12 h of strong stirring, centrifugation drying, finally collect solid sample；
4) two corundum are individually positioned in for 1:2 with mass ratio by black sample grind into powder obtained by step 3) and with Se powder In boat, in 10% vol H2It is calcined 5 hours in/90 vol %Ar atmosphere tube type furnaces in 800 oC, finally collects black powder sample Product derive porous carbon complex to get to tungsten selenide-collagen；
Using the derivative porous carbon complex of tungsten selenide-collagen of the present embodiment synthesis:: conductive agent acetylene black: binder According to electrode of working equably is coated on copper foil after 80: 10: 10 mixed grinding of mass percent, metallic sodium piece is CMC To electrode, the NaPF of 1 mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is that electrolyte is assembled into button electricity Pond；All assemblings carry 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 synthesis side of the derivative porous carbon complex anode material of lithium-ion battery of the tungsten selenide of excellent properties-collagen Method, steps are as follows:
1) the discarded ox-hide hair for weighing certain mass, is pre-processed, then shredded with scissors with EtOH Sonicate, and addition accounts for discarded ox-hide hair The enzyme preparation of quality 0.5% -1% dissolves, and the enzyme preparation uses pepsin/papain/trypsase, then It saltouts, finally freeze-drying grinds to obtain collagen protein powder；
2) collagen protein powder and zinc chloride are weighed in polytetrafluoroethyllining lining according to mass ratio 1:(0.2-2), are added suitable Water stirs 4-8 h, in N after drying21-2 h is activated in 500-900 oC with heating rate 5-10 oC/min in atmosphere tube type furnace, After washing and drying, black solid sample is collected；
3) the resulting black solid sample of step 2 and tungsten are weighed and adds a certain amount of distilled water in beaker, is vigorously stirred 6-12 h, centrifugation drying, finally collects solid sample；
4) it is 1:(1.5-3 with mass ratio by step 3) obtained solid sample grind into powder and with Se powder) it is individually positioned in two In corundum boat, in 10% vol H2It calcines 2-5 hours in/90 vol %Ar atmosphere tube type furnaces in 500-800 oC, finally collects Black powder sample derives porous carbon complex to get to tungsten selenide-collagen.
2. the derivative porous carbon complex sodium-ion battery of the tungsten selenide of excellent properties according to claim 1-collagen The synthetic method of negative electrode material, it is characterised in that: in step 1), the discarded ox-hide hair is from the discarded of leather industry Object, the collagen extracted from discarded ox-hide hair are rich in organic group, simultaneously containing a large amount of miscellaneous element, contain nitrogen, sulphur, energy It is converted in situ into N, S Heteroatom doping；In step 3), the tungsten source is serial tungsten salt, including is not limited to wolframic acid Sodium, tungsten chloride, phosphotungstic acid；The mass ratio of the collagen and tungsten source is 1:2-5, and the drying temperature is 80-100 ° C。
3. the derivative porous carbon of tungsten selenide-collagen of excellent properties made from any synthetic method of claim 1-2 Compound anode material of lithium-ion battery is the derivative porous carbon complex of tungsten selenide-collagen.
4. the derivative porous carbon complex sodium-ion battery of the tungsten selenide of excellent properties according to claim 3-collagen Negative electrode material, it is characterised in that: porous nano carbon complex derived from collagen has high voidage, and high-specific surface area is special Point, it is possible to provide a large amount of storage sodium active site simultaneously promotes electrolyte permeability to the inside of active material；Simultaneously by tungsten selenide particle Confinement is in porous nano carbon, stable structure, can volume change during buffer cycles；N in collagen, S element exist N can be converted in situ into calcination process, S Heteroatom doping, the electronic structure inside controllable derived carbon improves compound Electric conductivity.
5. the derivative porous carbon of tungsten selenide-collagen of excellent properties made from any synthetic method of claim 1-2 Compound anode material of lithium-ion battery is the application of the derivative porous carbon complex of tungsten selenide-collagen, it is characterised in that: institute The derivative porous carbon complex of the tungsten selenide stated-collagen is applied in sodium-ion battery cathode, voltage be 0.01-3.0 V, Charge and discharge cycles 50 times when current density is 100 mA/g, specific capacity is up to 368.2 mAh/g, in 1 A/g of high current density After charge and discharge cycles 500 times, specific capacity remains at 185.5 mAh/g, coulombic efficiency with higher, while also having excellent High rate performance.
6. a kind of sodium-ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: claim 1-2 appoints The derivative porous carbon complex sodium-ion battery cathode of the tungsten selenide of excellent properties made from synthetic method described in one-collagen Material: electricity of working conductive agent acetylene black: is uniformly coated on copper foil after CMC=80: 10: 10 mixed grinding of binder Pole, metallic sodium piece are to electrode, the NaPF of 1 mol/L6/ ethylene carbonate (EC)+diethyl carbonate (DEC) is electrolysis Liquid is assembled into 2032 type button-type batteries.
CN201910415732.XA 2019-05-18 2019-05-18 Synthesis method and application of tungsten selenide-collagen derived porous carbon composite sodium ion battery cathode material with excellent performance Active CN110265637B (en)

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