CN109698337A - Sulphur-spore carbon/niobium carbide combination electrode material and its preparation method and application - Google Patents
Sulphur-spore carbon/niobium carbide combination electrode material and its preparation method and application Download PDFInfo
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- CN109698337A CN109698337A CN201811583142.XA CN201811583142A CN109698337A CN 109698337 A CN109698337 A CN 109698337A CN 201811583142 A CN201811583142 A CN 201811583142A CN 109698337 A CN109698337 A CN 109698337A
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H—ELECTRICITY
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- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention discloses a kind of sulphur-spore carbon/niobium carbide combination electrode materials and its preparation method and application, comprising: obtains reesei spores;By 6h, 9h and 12h solvent-thermal method and high temperature cabonization have synthesized spore carbon/niobium carbide composite material, and as carrier, by melting sulfurizing method, reaction 12-16h is compound with elemental sulfur progress, obtain sulphur-spore carbon/niobium carbide composite electrode.Sulphur of the present invention-spore carbon/niobium carbide composite electrode is three-dimensional porous structure, specific surface area with higher, higher high circulation stability, the features such as high rate performance and coulombic efficiency, particularly suitable as lithium sulfur battery anode material, the anode composite improves the high rate performance and cycle performance of lithium sulphur, facilitate promote high-energy density, high stability lithium-sulfur cell development.
Description
Technical field
The present invention relates to lithium sulfur battery anode material fields, and in particular to a kind of sulphur-spore carbon/niobium carbide combination electrode material
Material and preparation method thereof and as lithium sulfur battery anode material application.
Background technique
At this stage, lithium ion battery is that most commonly used battery is used in commercialization.However, with electric car and high-quality
The continuous development of power equipment is measured, the energy density of lithium ion battery can be only sustained at 200~250Wh/kg, have been unable to meet height
The demand of energy density batteries.Therefore, the high energy density cells material for exploring new remote super lithium ion battery becomes increasingly
It is important.Lithium-sulfur cell, the bulk density of energy density and 2800Wh/L with 2600Wh/kg, causes extensive concern.Sulphur
Anode has the theoretical capacity of 1675mAh/g, and cheap, environmental-friendly, has very big commercial applications prospect.But
It is that lithium-sulfur cell haves the defects that some intrinsic to limit its development: elemental sulfur and its electrochemical products lithium sulfide electronics electricity
Conductance is lower, is electrons/ions insulator, reduces electrochemical reaction rates, reduces the utilization rate of active material sulphur;Cyclic process
Middle generation volume change reduces electrode cycle stability;The shuttle effect of intermediate product (polysulfide), leads to irreversible capacity
Generation, and reduce coulombic efficiency.
Aiming at the problem that appearing above, scientific research personnel mainly carries out the sulphur anode of lithium-sulfur cell using following several strategies
It is modified: high conductivity substance, such as carbon material are used, it is compound with the progress of active material sulphur, improve the electron conduction of electrode;With pole
Property sulfide, carbide, nitride etc. carry out compound, suction-operated is generated to polarity polysulfide, inhibits wearing for polysulfide
Shuttle effect;Porous structure, including mesoporous, micropore etc. are constructed, the contact area of electrode material and electrolyte is improved, increases the benefit of sulphur
With rate, chemical property is improved.Therefore, it carries out compound being a kind of more effective method of modifying with the carbon material of high conductivity.
Meanwhile it constructing porous structure and will further improve its chemical property.Therefore, it invents one kind and is suitble to large-scale production, electric conductivity
High porous carbon materials are very important, and improve the preferred approach of lithium-sulfur cell performance.
Summary of the invention
For the problems in background technique, the purpose of the present invention is to provide a kind of sulphur-spore carbon/niobium carbide combination electrodes
Material and its preparation method and application synthesizes sulphur-spore carbon/niobium carbide combination electrode material of high capacity, passes through high conductivity
Spore carbon substrate and polarity niobium carbide nano particle carry out collaboration optimization, inhibit the shuttle problem of polysulfide, improve lithium sulphur
The multiplying power and cycle performance of battery.
A kind of sulphur-spore carbon/niobium carbide combination electrode material preparation method, includes the following steps:
(1) reesei spores are obtained;
(2) it takes reesei spores to be placed in acetone to impregnate, filtering, removal is then cleaned in dehydrated alcohol and deionized water
The grease on its surface, is dried in an oven, the spore after being dried;
(3) by 200 DEG C in air~400 DEG C 3~9h of the pre-heat treatment of the spore after drying, then in Ar atmosphere is enclosed
600 DEG C~800 DEG C heat treatment 1h~5h obtain reesei spores carbon (high conductivity) after cooling;
(4) NbCl is configured5Ethanol solution weighs reesei spores carbon and pours into NbCl5It uniformly mixes in ethanol solution, then turns
Move on to 150~250 DEG C of 3~9h of reaction in hydrothermal reaction kettle;
(5) after reaction, it by the powder deionized water and washes of absolute alcohol of acquisition and dries, after drying, by powder
Loaded on tube furnace is transferred in quartz boat, 720 DEG C under an argon atmosphere~880 DEG C are heat-treated 1~4h and 920 DEG C~1080 DEG C at end
It is heat-treated 1~4h, after cooling, obtains spore carbon/niobium carbide composite material;
(6) spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, heating
It to 100~190 DEG C, reacts 10~18 hours, after reaction kettle cooling, takes out reaction product, obtain sulphur-spore carbon/niobium carbide
Composite material.
It is used as the preferred technical solution of the present invention below:
In step (1), reesei spores are obtained, comprising:
With one of cotton seed hulls, sawdust, Duan Mu or it is a variety of (two or three) be nutrients, using PDA culture medium
(Potato Dextrose Agar) plate culture is sprouted in 22 DEG C~26 DEG C, the environment that relative humidity is 90%~98%,
After culture 3~5 days, colony diameter is 8.1~9.0 centimetres, acquires resulting reesei spores.
In step (2), the reesei spores, acetone the ratio between dosage for 10g:30~70ml (further preferably
10g:50ml).
The time of the immersion is 5~7h (further preferably 6h).
The temperature of the drying is 60~80 DEG C (further preferably 70 DEG C).
In step (3), by 250 DEG C in air~350 DEG C 5~7h of the pre-heat treatment of the spore after drying, (preferably 300 DEG C pre-
It is heat-treated 6h), removal mycotic spore itself existing cell liquid, fat etc. are then transferred into tube furnace and enclose in Ar atmosphere
In 650 DEG C~750 DEG C 1~3h of heat treatment (preferably 700 DEG C heat treatment 2h), heating rate be 5~15 DEG C/min (preferably 10 DEG C/
Min), after cooling, reesei spores carbon (high conductivity) is obtained.
In step (4), NbCl is configured5Ethanol solution weighs reesei spores carbon and pours into NbCl5It is uniformly mixed in ethanol solution,
It is subsequently transferred to 180~220 DEG C of 5~7h of reaction (further preferred 200 DEG C of reactions 6h) in hydrothermal reaction kettle;
The NbCl5NbCl in ethanol solution5Concentration be 0.5~3mmol/L, further preferably 1mmol/L,
The reesei spores carbon and NbCl5The ratio between dosage of ethanol solution is 1~5g:40~80mL (further preferred
For 2g:60mL).
It in step (5), after reaction, by the powder deionized water and washes of absolute alcohol of acquisition and dries, dries
Afterwards, by powder loaded on tube furnace is transferred in quartz boat, 770 DEG C under an argon atmosphere~830 DEG C are heat-treated 1~3h and 970 DEG C
~1030 DEG C of 1~3h of heat treatment, after cooling, obtain spore carbon/niobium carbide composite material;
Most preferably, after reaction, it is dried by the powder of acquisition deionized water and washes of absolute alcohol and at 60 DEG C
It is dry, after drying, powder is loaded in quartz boat and is transferred to tube furnace, under an argon atmosphere 2h and 1000 DEG C of heat of 800 DEG C of heat treatment
2h is handled, heating rate is 5 DEG C/min, after cooling, obtains spore carbon/niobium carbide composite material;
In step (6), spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave
In, be heated to 120~170 DEG C, react 12~16 hours, after reaction kettle cooling, take out reaction product, obtain sulphur-spore carbon/
Niobium carbide composite material.
Most preferably, the sulphur-spore carbon/niobium carbide combination electrode material preparation method, includes the following steps:
(1) with one of cotton seed hulls, sawdust, Duan Mu or it is a variety of (two or three) be nutrients, using PDA culture medium
(Potato Dextrose Agar) plate culture is sprouted in 24 DEG C, the environment that relative humidity is 95%, after culture 4 days, bacterium
Falling diameter is 8.1~9.0 centimetres, acquires resulting reesei spores;
(2) it takes 10g reesei spores to be placed in the acetone of 50mL and impregnates 6h, it is then clear in dehydrated alcohol and deionized water
Filter is washed, the grease on its surface is removed, is dried in 70 DEG C of baking oven, the spore after being dried;
(3) by the spore after drying, 300 DEG C of the pre-heat treatment 6h (remove cell existing for mycotic spore itself in air
Liquid, fat etc.), 700 DEG C of heat treatment 2h in Ar atmosphere is enclosed are then transferred into tube furnace, heating rate is 10 DEG C/min,
After cooling, reesei spores carbon (high conductivity) is obtained;
(4) NbCl of 60mL 1mmol/L is configured5Ethanol solution, stirs 30min, and the reesei spores carbon for weighing 2g pours into
NbCl5It is uniformly mixed in ethanol solution, is subsequently transferred to 200 DEG C of reaction 6h in hydrothermal reaction kettle;
(5) after reaction, it dries, dries by the powder of acquisition deionized water and washes of absolute alcohol and at 60 DEG C
Afterwards, powder is heat-treated 2h for 800 DEG C and 1000 DEG C under an argon atmosphere loaded on tube furnace is transferred in quartz boat respectively, is heated up
Speed is 5 DEG C/min, after cooling, obtains spore carbon/niobium carbide composite material;
(6) spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, heating
To 120~170 DEG C, the reaction time is 12~16 hours, after reaction kettle cooling, takes out reaction product, obtain sulphur-spore carbon/
Niobium carbide composite material.
The sulphur of high capacity-spore carbon/niobium carbide combination electrode material, reesei spores carbon, carbon including nitrogen and phosphor codoping
Change niobium nano particle and active material sulphur.The sulphur-spore carbon/niobium carbide combination electrode material, with the nickel being evenly distributed
(2-3 μm) of reesei spores carbon with phosphorus doping is major bases, and solvent thermal growth coats niobium carbide nano particle, while generating big
The hole of amount forms porous structure, and niobium carbide nano particle size is 25-30nm, pore size 30-50nm.
The sulphur of high capacity-spore carbon/niobium carbide combination electrode material can be used for inhibiting lithium-sulfur cell shuttle effect, improve electricity
Pole ion/electron conductivity, the material are carrier, collaboration optimization by reesei spores carbon and the niobium carbide nano particle of high conductivity
The chemical property of sulphur anode, is highly suitable as lithium sulfur battery anode material.
The present invention has the following advantages that compared with the prior art and protrudes effect:
In the present invention, sulphur-spore carbon/niobium carbide combination electrode material, as main carriers, is had using reesei spores carbon
The nitrogen and P elements adulterated in situ improves the absorption to polysulfide, to reduce the irreversible capacity in cyclic process;Using
The niobium carbide nano particle of high conductivity accelerates interfacial reaction as chemisorbed material, increases electronics transport channel, to mention
Its high chemical property;At the same time, in niobium carbide nano particle forming process, porous structure is obtained, increases the ratio table of carrier
Area improves the utilization rate of active material sulphur.The anode composite improves the high rate performance and cycle performance of lithium sulphur, helps to push away
Into the development of high-energy density, the lithium-sulfur cell of high stability.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of spore carbon/niobium carbide composite material obtained in embodiment 3.
Fig. 2 is the transmission electron microscope picture of spore carbon/niobium carbide composite material obtained in embodiment 3.
Fig. 3 is the Elemental redistribution spectrogram of spore carbon/niobium carbide composite material obtained in embodiment 3, wherein a is in Fig. 3
The total distributed spectrogram of each element in composite material, b is the total distributed spectrogram of each element in composite material in Fig. 3, and c is multiple in Fig. 3
The distribution spectrogram of C element in condensation material, d is the distribution spectrogram of the distribution spectrogram of Nb element in composite material in Fig. 3, and e is in Fig. 3
The distribution spectrogram of P element in composite material, f is the distribution spectrogram of N element in composite material in Fig. 3;
Fig. 4 is sulphur-spore carbon/niobium carbide combination electrode material scanning electron microscope (SEM) photograph obtained in embodiment 3.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
(1) with cotton seed hulls, sawdust, Duan Muwei nutrients, PDA culture medium, Potato (are used using PDA plate cultivation
Dextrose Agar), it is sprouted in 24 DEG C, the environment that relative humidity is 95%.After culture 4 days, colony diameter is 8.1~9.0
Centimetre, acquire resulting reesei spores.
(2) it takes 10g reesei spores to be placed in the acetone of 50ml and impregnates 6h, it is then clear in dehydrated alcohol and deionized water
Filter is washed, the grease on its surface is removed, is dried in 70 DEG C of baking oven, the spore after being dried.
(3) by the 300 DEG C of heat treatment 6h in air of the spore after drying, cell liquid existing for removal mycotic spore itself,
Fat etc..Later, 700 DEG C of heat treatment 2h (Ar atmosphere is enclosed) in tube furnace are transferred to, heating rate is 10 DEG C/min.It is cooling
Afterwards, mycotic spore carbon (high conductivity) is obtained.
(4) NbCl of 60ml 1mmol/L is configured5Ethanol solution stirs 30min.The mycotic spore carbon for weighing 2g pours into this
It is uniformly mixed in solution, is subsequently transferred to 200 DEG C of reaction 6h in hydrothermal reaction kettle.
(5) it after hydro-thermal reaction, dries the powder of acquisition deionized water and washes of absolute alcohol 3 times and at 60 DEG C
It is dry.After drying, by powder loaded on tube furnace is transferred in quartz boat, locate respectively at 800 DEG C and 1000 DEG C under an argon atmosphere
2h is managed, heating rate is 5 DEG C/min.After cooling, spore carbon/niobium carbide composite material can be obtained.
(6) spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, heating
To 120~170 DEG C, the reaction time is 12~16 hours, after reaction kettle cooling, takes out reaction product, obtain sulphur-spore carbon/
Niobium carbide composite material.
Embodiment 1
Using cotton seed hulls as nutrients, reesei spores are obtained, weigh 2.0g reesei spores carbon in hydrothermal reaction kettle.Utilize five
Niobium chloride (NbCl5) as presoma 200 DEG C of solvent thermal reaction 6h of progress, furnace cooling.Gained sample deionized water and nothing
Water-ethanol is cleaned for several times and is dried, and under argon atmosphere, handles 2h at 800 DEG C and 1000 DEG C respectively, heating rate is 5
DEG C/min, obtain spore carbon/niobium carbide composite material.Spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, then
It is placed in autoclave, is heated to 120~140 DEG C, the reaction time is 16 hours, after reaction kettle cooling, takes out reaction and produces
Object obtains sulphur-spore carbon/niobium carbide composite material.
Embodiment 2
Using sawdust as nutrients, reesei spores are obtained, weigh 2.0g reesei spores carbon in hydrothermal reaction kettle.Utilize pentachloro-
Change niobium (NbCl5) as presoma 200 DEG C of solvent thermal reaction 9h of progress, furnace cooling.Gained sample deionized water and anhydrous
Ethyl alcohol cleaning for several times and is dried, and under argon atmosphere, handles 2h at 800 DEG C and 1000 DEG C respectively, and heating rate is 5 DEG C/
Min obtains spore carbon/niobium carbide composite material.Spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then set
Entering in autoclave, is heated to 140~150 DEG C, the reaction time is 14 hours, after reaction kettle cooling, reaction product is taken out,
Obtain sulphur-spore carbon/niobium carbide composite material.
Embodiment 3
With Duan Muwei nutrients, reesei spores are obtained, weigh 2.0g reesei spores carbon in hydrothermal reaction kettle.Utilize pentachloro-
Change niobium (NbCl5) as presoma 200 DEG C of solvent thermal reaction 12h of progress, furnace cooling.Gained sample deionized water and anhydrous
Ethyl alcohol cleaning for several times and is dried, and under argon atmosphere, handles 2h at 800 DEG C and 1000 DEG C respectively, and heating rate is 5 DEG C/
Min obtains spore carbon/niobium carbide composite material.Spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then set
Entering in autoclave, is heated to 160~170 DEG C, the reaction time is 12 hours, after reaction kettle cooling, reaction product is taken out,
Obtain sulphur-spore carbon/niobium carbide composite material.
Performance test
It is pair that sulphur made of above-described embodiment 1~3-spore carbon/niobium carbide composite material, which is assembled into lithium metal disk,
The half-cell of electrode carries out electro-chemical test, and the LiTFSI+DOL/DME (1:1) of 1M is electrolyte.By anode pole piece, electrolyte,
Diaphragm, lithium piece, which sequentially add, carries out battery assembly in anode cover, battery is compressed to sealing after assembling in full-automatic sealing machine,
After standing for 24 hours, electro-chemical test is carried out using blue electricity and electrochemical workstation.Electro-chemical test is in 25 DEG C of constant temperature
Lower progress mainly includes constant current charge-discharge test and cyclic voltammetry.It is main packet in test in constant current charge-discharge test
Include the indexs such as specific capacity, high rate performance, cycle performance, coulombic efficiency.Battery testing voltage range is relative to Li/Li+~
1.7-2.8V, Rate test currents 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, loop test electric current are 0.2C.
The performance test results are as follows:
The sulphur of embodiment 1, embodiment 2 and embodiment 3-spore carbon/niobium carbide composite electrode is followed in 0.2C charge and discharge
Under ring, initial discharge capacity is respectively 1011mAh/g, 1189mAh/g and 1230mAh/g.In addition, after 500 circle circulation of circulation, three
The specific discharge capacity conservation rate of kind electrode is up to 60%, and coulombic efficiency is up to 95% or more.As it can be seen that sulphur-spore obtained above
The discharge capacity of the cell that carbon/niobium carbide composite electrode is constituted is high, good cycling stability, and coulombic efficiency is high.Embodiment
1, preferable knot is also obtained in the sulphur of embodiment 2 and embodiment 3-spore carbon/niobium carbide composite electrode high rate performance test
Fruit, under 5C current density, electric discharge specific capacitance is respectively 598mAh/g, 608mAh/g and 789mAh/g.As it can be seen that obtained above
Sulphur-spore carbon/niobium carbide composite electrode is had excellent performance in high current charge-discharge.
Sulphur-spore carbon/niobium carbide composite electrode is porous structure, increases the load capacity of active material sulphur, also increases
The contact area of electrode surface and electrolyte is added;Reesei spores carbon and niobium carbide nano particle all have higher electronics and conduct
Rate improves the electric conductivity of electrode, accelerates interfacial reaction;Reesei spores carbon has the phosphorus adulterated in situ and nitrogen, provides more sulphur
The adsorption site of compound cooperates with the shuttle effect for inhibiting polysulfide with polarity niobium carbide nano particle, to improve electrode
Multiplying power and cycle performance.
Therefore, sulphur of the present invention-spore carbon/niobium carbide composite electrode have high circulation stability, high rate capability and
The features such as coulombic efficiency, the lithium sulfur battery anode material for making it be expected to become the high-energy density of energy commercial applications.
Claims (10)
1. a kind of sulphur-spore carbon/niobium carbide combination electrode material preparation method, which comprises the steps of:
(1) reesei spores are obtained;
(2) it takes reesei spores to be placed in acetone to impregnate, filtering is then cleaned in dehydrated alcohol and deionized water, removes its table
The grease in face, is dried in an oven, the spore after being dried;
(3) by 200~400 DEG C of 3~9h of the pre-heat treatment in air of the spore after drying, then 600~800 in Ar atmosphere is enclosed
DEG C 1~5h of heat treatment obtains reesei spores carbon after cooling;
(4) NbCl is configured5Ethanol solution weighs reesei spores carbon and pours into NbCl5It uniformly mixes, is subsequently transferred in ethanol solution
150~250 DEG C of 3~9h of reaction in hydrothermal reaction kettle;
(5) after reaction, it by the powder deionized water and washes of absolute alcohol of acquisition and dries, after drying, powder is filled
Tube furnace is transferred in quartz boat, under an argon atmosphere 720~880 DEG C of heat treatment, 1~4h and 920~1080 DEG C of heat treatment 1
~4h after cooling, obtains spore carbon/niobium carbide composite material;
(6) spore carbon/niobium carbide composite material is uniformly mixed with sulphur simple substance, is then placed in autoclave, is heated to 100
It~190 DEG C, reacts 10~18 hours, after reaction kettle cooling, takes out reaction product, obtain sulphur-spore carbon/niobium carbide composite wood
Material.
2. preparation method according to claim 1, which is characterized in that in step (1), obtain reesei spores, comprising:
With one of cotton seed hulls, sawdust, Duan Mu or a variety of for nutrients, using PDA culture medium plate culture, 22 DEG C~26
DEG C, it is sprouted in the environment that relative humidity is 90%~98%, after culture 3~5 days, colony diameter is 8.1~9.0 centimetres, acquisition
Resulting reesei spores.
3. preparation method according to claim 1, which is characterized in that in step (2), the reesei spores, acetone
The ratio between dosage is 10g:30~70mL;
The time of the immersion is 5~7h;
The temperature of the drying is 60~80 DEG C.
4. preparation method according to claim 1, which is characterized in that in step (3), in air by the spore after drying
250~350 DEG C of 5~7h of the pre-heat treatment, be then transferred into tube furnace in Ar atmosphere is enclosed 650 DEG C~750 DEG C heat treatments 1~
3h obtains reesei spores carbon after cooling.
5. preparation method according to claim 1, which is characterized in that in step (4), configure NbCl5Ethanol solution weighs
Reesei spores carbon pours into NbCl5Uniformly mixed in ethanol solution, be subsequently transferred in hydrothermal reaction kettle 180~220 DEG C of reactions 5~
7h。
6. preparation method according to claim 1, which is characterized in that in step (4), the NbCl5In ethanol solution
NbCl5Concentration be 0.5~3mmol/L;
The reesei spores carbon and NbCl5The ratio between dosage of ethanol solution is 1~5g:40~80mL.
7. preparation method according to claim 1, which is characterized in that in step (5), after reaction, by the powder of acquisition
End deionized water and washes of absolute alcohol are simultaneously dried, after drying, by powder loaded on tube furnace is transferred in quartz boat, in argon gas
1~3h and 970 DEG C~1030 DEG C 1~3h of heat treatment of lower 770 DEG C~830 DEG C of atmosphere heat treatment, after cooling, obtain spore carbon/carbon
Change niobium composite material.
8. preparation method according to claim 1, which is characterized in that in step (6), by spore carbon/niobium carbide composite wood
Material is uniformly mixed with sulphur simple substance, is then placed in autoclave, is heated to 120~170 DEG C, is reacted 12~16 hours, to anti-
After answering kettle to cool down, reaction product is taken out, sulphur-spore carbon/niobium carbide composite material is obtained.
9. sulphur-spore carbon/niobium carbide the combination electrode material prepared according to the described in any item preparation methods of right 1~8.
10. the sulphur according to right 9-spore carbon/niobium carbide combination electrode material is as lithium sulfur battery anode material.
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CN114057230A (en) * | 2021-11-19 | 2022-02-18 | 电子科技大学长三角研究院(湖州) | Penicillium spore carbon/manganese dioxide composite material and preparation method and application thereof |
CN116143246A (en) * | 2023-03-09 | 2023-05-23 | 北京市生态环境保护科学研究院 | Preparation method of Aspergillus niger spore electrode active material based on micro-nano structure |
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CN113644284A (en) * | 2021-07-08 | 2021-11-12 | 广东工业大学 | Carbon material loaded fluorine-doped niobium carbide nano composite material and preparation method and application thereof |
CN114057230A (en) * | 2021-11-19 | 2022-02-18 | 电子科技大学长三角研究院(湖州) | Penicillium spore carbon/manganese dioxide composite material and preparation method and application thereof |
CN114057230B (en) * | 2021-11-19 | 2024-01-30 | 电子科技大学长三角研究院(湖州) | Penicillium spore carbon/manganese dioxide composite material and preparation method and application thereof |
CN116143246A (en) * | 2023-03-09 | 2023-05-23 | 北京市生态环境保护科学研究院 | Preparation method of Aspergillus niger spore electrode active material based on micro-nano structure |
CN116143246B (en) * | 2023-03-09 | 2024-03-26 | 北京市生态环境保护科学研究院 | Preparation method of Aspergillus niger spore electrode active material based on micro-nano structure |
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