CN104993111A - Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof - Google Patents
Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof Download PDFInfo
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Abstract
The invention discloses a manganese dioxide/nitrating carbon fiber cathode composite material for a sodium-ion battery and a preparing method thereof. The cathode material is a composite material formed after manganese dioxide evenly grows on the surface of nitrating carbon fiber. The preparing method comprises the steps of breaking a bacterial cellulose film through stirring to form uniform turbid liquid, adding an ammonium salt and urea solution to the bacterial cellulose turbid liquid, stirring for reaction, and obtaining nitrating carbon fiber through high-heat treatment after a product is freeze-dried; acidizing nitrating carbon fiber to enable nitrating carbon fiber to be evenly dispersed in an aqueous solution, adding potassium permanganate and sodium sulfate, and stirring at the room temperature for reaction, so that the cathode composite material with nitrating carbon fiber evenly coated with manganese dioxide is obtained. The preparing method is reliable, technology repeatability is high, operability is high, cost is low, and the preparing method is suitable for industrial production. The composite material has excellent electrochemical performance when applied to the sodium-ion battery.
Description
Technical field
The invention belongs to sodium-ion battery field, be specifically related to a kind of manganese dioxide for sodium-ion battery/nitrating carbon fiber negative material and preparation method thereof.
Background technology
Past three, the battery of lithium ion was fast-developing during the decade, the mobile device Battery Market such as PC, video camera, mobile phone that made it dominate.And along with the application prospect that electric motor car, hybrid vehicle aspect are good, the demand of lithium battery constantly increases, be subject to lithium price, store quantitative limitation, lithium ion battery developed into the bottleneck phase.Sode cell receives extensive concern because resource reserves are abundant, cost is low, and the research and development of sodium-ion battery can relax the battery development limitation problem because lithium resource shortage causes to a certain extent.But due to the ionic radius (0.102nm) of sodium ion more much larger than the ionic radius (0.76nm) of lithium ion, make sodium ion embed in battery material with deviate from more difficult than lithium ion.The electrode material of some lithium ion batteries as desirable in Graphene etc. is not also suitable for sodium-ion battery, and the research of sodium-ion battery is also early stage in its its development.Thus, exploitation excellent performance, cheap sodium-ion battery positive and negative pole material seem particularly important.This is also a research emphasis from now on, is a significant challenge of current sodium-ion battery development.
Manganese dioxide (MnO
2) be a kind of important VIIB-VIA compound semiconductor, different crystal forms, rich content, environmental friendliness and chemically stable material is had as one, be widely used in fields such as electrolytic lead zinc, glass, pottery, medicine and batteries, but manganese dioxide is as sodium cell negative pole material then rare people's report.Research finds, MnO
2also have very high theory storage sodium specific capacity, but due to itself electrons/ions conductivity very low, and there is serious volumetric expansion in the process of deintercalation sodium, cause its cyclical stability extremely low.
Summary of the invention
The present invention is directed to the defect that existing sodium-ion battery material exists, there is provided a kind of cost low, manganese dioxide homoepitaxial at nitrating carbon fiber surface, for the manganese dioxide/nitrating carbon fiber anode material of high charge-discharge specific capacity, good high rate performance and cycle performance can be obtained in sodium-ion battery.
Another object of the present invention is the preparation method being to provide simple, reproducible, with low cost, the eco-friendly above-mentioned composite material of a kind of technique.
Technical scheme of the present invention:
The invention provides the anode material of a kind of manganese dioxide for sodium-ion battery/nitrating carbon fiber, this composite material is the anode material of the even coated nitrating carbon fiber of manganese dioxide, preparation method, for be blended by bacteria cellulose film, makes it form uniform suspension-turbid liquid; In bacteria cellulose suspension-turbid liquid, add the mixed solution of ammonium salt solution and urea liquid, stirring reaction, after freeze drying, heat treatment obtains nitrating carbon fiber; Acidification nitrating carbon fiber, it is in aqueous dispersed, then add permanganate and sulfate, stirred at ambient temperature reacts, and after washing drying, obtains manganese dioxide/nitrating carbon fiber anode material.
The diameter of manganese dioxide/nitrating carbon fiber anode material is preferably 100 ~ 400nm.
Manganese dioxide/nitrating carbon fiber anode material specific area is preferably 100 ~ 700m
2g
-1.
In manganese dioxide/nitrating carbon fiber anode material, nitrogen content is preferably 2 ~ 10wt%.
In preferred manganese dioxide/nitrating carbon fiber anode material, the quality of manganese dioxide accounts for 50 ~ 90% of manganese dioxide and nitrating carbon fiber gross mass.
Present invention also offers the preparation method of the anode material of a kind of manganese dioxide for sodium-ion battery/nitrating carbon fiber, preparation method, for be blended by bacteria cellulose film, makes it form uniform suspension-turbid liquid; In bacteria cellulose suspension-turbid liquid, add the mixed solution of ammonium salt solution and urea liquid, stirring reaction, after freeze drying, heat treatment obtains nitrating carbon fiber; Acidification nitrating carbon fiber, it is in aqueous dispersed, then add permanganate and sulfate, stirred at ambient temperature reacts, and after washing drying, obtains manganese dioxide/nitrating carbon fiber anode material.
Preferred preparation method is: blended by bacteria cellulose film, make it form uniform suspension-turbid liquid, in suspension-turbid liquid, add the mixed solution of ammonium salt solution and urea liquid, stirring reaction 10 ~ 24h, product through 25 ~ 30h freeze drying, obtains nitrating bacteria cellulose at-20 ~-60 DEG C; Under inert atmosphere protection, with the heating rate of 1 ~ 10 DEG C/min, temperature is risen to 500 ~ 800 DEG C, after insulation 2 ~ 10h, obtain nitrating carbon fiber; After the concentrated sulfuric acid and concentrated nitric acid solution acidification nitrating carbon fiber, then joined deionized water for ultrasonic dispersion and obtained dispersion liquid, in dispersion liquid, added permanganate and sulfate and after fully dissolving, stirring at room temperature reaction 1 ~ 5h; Product, after washing, 60 ~ 90 DEG C of dryings, obtains manganese dioxide/nitrating carbon fiber anode material.
In above-mentioned preparation method, the further preferably freeze drying time is 25 ~ 30h.
The stirring reaction time adding potassium permanganate and sodium sulphate is preferably 1 ~ 5h.
Described ammonium salt is preferably selected from one or more in ammonium chloride, ammonium sulfate, ammonium carbonate or carbonic hydroammonium.
The concentration of ammonium salt solution is preferably 0.01 ~ 0.1mol/L.
The concentration of urea liquid is preferably 0.01 ~ 0.1mol/L.
The volume ratio of ammonium salt solution and urea liquid is preferably 1 ~ 3:1.
The method of acidification is nitrating carbon fiber is dispersed in volume ratio to be preferably in the concentrated sulfuric acid of 1:1 ~ 3 and the solution of red fuming nitric acid (RFNA).
The stirring reaction time of acidification is preferably 8 ~ 12h.
The mol ratio of preferred permanganate and sulfate is 1:1 ~ 4.
The mass ratio of nitrating carbon fiber and permanganate is preferably 1:1 ~ 4.
Described permanganate be preferably selected from potassium permanganate or sodium permanganate one or both.
Described sulfate be preferably selected from sodium sulphate or manganese sulfate one or both.
Beneficial effect of the present invention:
The invention provides a kind of manganese dioxide homoepitaxial at nitrating carbon fiber surface, for the manganese dioxide/nitrating carbon fiber anode material of high charge-discharge specific capacity, good high rate performance and long circulation life can be obtained in sodium-ion battery.Nitrating carbon fiber in the present invention has interconnective network configuration, manganese dioxide homoepitaxial is on nitrating carbon fiber, this structure also can be kept, nitrating carbon fiber is that sodium-ion battery provides effective conductive network and sodium ions passage, ensure that good ion transport capability, be applied in sodium ion and show excellent performance.The present invention, by doping nitrogen and acidification carbon fiber, makes carbon fiber surface have abundant functional group, further ensure that manganese dioxide is at the homoepitaxial of carbon fiber surface and better chemical property.In addition, the preparation method of manganese dioxide of the present invention/nitrating carbon fiber anode material is simple, reproducible, with low cost, and environmental friendliness is applicable to suitability for industrialized production.Composite material born by the manganese dioxide that the method prepares/nitrating carbon fiber, during as anode material of lithium-ion battery, has very high charging and discharging capacity and good cycle performance.
Accompanying drawing explanation
The scanning electron microscope (SEM) photograph (SEM) that [Fig. 1] is manganese dioxide in embodiment 1/nitrating carbon fibre composite.
The scanning electron microscope (SEM) photograph (SEM) that [Fig. 2] is manganese dioxide in comparative example 1/nitrating carbon fibre composite.
The scanning electron microscope (SEM) photograph (SEM) that [Fig. 3] is manganese dioxide/Carbon Nanofibers/Epoxy Resin Composite Materials in comparative example 2.
The x-ray diffraction pattern (XRD) that [Fig. 4] is manganese dioxide in embodiment 1/nitrating carbon fibre composite.
Sodium-ion battery 100 cyclic discharge capacity curve charts of the manganese dioxide that [Fig. 5] obtains for embodiment 1/nitrating carbon fiber anode material assembling.
The high rate performance figure of the sodium-ion battery of the manganese dioxide that [Fig. 6] obtains for embodiment 1/nitrating carbon fiber anode material assembling.
Embodiment
Following examples are intended to be described in further details content of the present invention; And the protection range of the claims in the present invention does not limit by embodiment.
Embodiment 1
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business, blending bacteria cellulose film makes it form uniform suspension-turbid liquid, get 100mL bacteria cellulose suspension-turbid liquid and add 50mL ammonium chloride solution (0.1mol/L) and 50mL urea liquid (0.1mol/L) stirring reaction 20h, after filtering and washing, at-48 DEG C of temperature, freeze drying example 25h obtains nitrating bacteria cellulose.Be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, temperature risen to 600 DEG C, after insulation 2h, obtain nitrating carbon fiber.With the 100mL concentrated sulfuric acid and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidification 10h nitrating carbon fibers, product is through washing, drying, obtain the nitrating carbon fiber of acidification, getting the nitrating carbon fiber after 0.1g acidification is dispersed in the deionized water of 150mL, ultrasonic 40min obtains uniform dispersion liquid, 0.3g potassium permanganate and 0.27g sodium sulphate is added again, stirred at ambient temperature reaction 1h in dispersion liquid.Product is through washing, drying in the baking oven of 80 DEG C, and obtaining specific area is 600m
2g
-1, composite material diameter to be 100 ~ 270nm and nitrogen mass percentage be 6% manganese dioxide/nitrating carbon fiber anode material.
Take a certain amount of above-mentioned obtained manganese dioxide/nitrating carbon fiber negative material, add 10% conductive black as conductive agent, 10% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1M NaClO
4/ EC:DEC (1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
The sode cell electrode adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and its chemical property is as shown in Fig. 5 ~ 6:
Can find out in Fig. 1 that manganese dioxide homoepitaxial is at nitrating carbon fiber surface, composite material is in presenting interconnective network configuration, and the diameter of composite material is 100 ~ 270nm.
Can find out in Fig. 4 that position and the relative intensity of each diffraction maximum in manganese dioxide/nitrating carbon fiber negative material all match with JCPDS (JCPDS) card (80-1098), show that product is rhombic MnO
2.
Show the electrode adopting manganese dioxide/nitrating carbon fiber negative material to make in Fig. 5, at room temperature when 500mA/g constant-current discharge, circulation 100 circle specific capacity still can remain on 355mA h/g; Show good cycle performance.
Show in Fig. 6 that the high rate performance of electrode respective battery under different discharge-rate adopting manganese dioxide/nitrating carbon fiber negative material to make is bent, can find that this composite material has excellent high rate performance, under large multiplying power 2000mA/g, capacity still can remain on 314mA h/g, and after current density slowly gets back to 500mA/g by big current, capacity is returned to again 346.1mA h/g.
Embodiment 2
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business, blending bacteria cellulose film makes it form uniform suspension-turbid liquid, get 100mL bacteria cellulose suspension-turbid liquid and add 100mL ammonium sulfate (0.05mol/L) and 50mL urea liquid (0.05mol/L) stirring reaction 18h, after filtering and washing, at-50 DEG C of temperature, freeze drying example 30h obtains nitrating bacteria cellulose.Be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 3 DEG C/min, temperature risen to 500 DEG C, after insulation 3h, obtain nitrating carbon fiber.With the 100mL concentrated sulfuric acid and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidification 8h nitrating carbon fibers, product is through washing, drying, obtain the nitrating carbon fiber of acidification, getting the nitrating carbon fiber after 0.15g acidification is dispersed in the deionized water of 250mL, ultrasonic 60min obtains uniform dispersion liquid, 0.45g potassium permanganate and 0.4g sodium sulphate is added again, stirred at ambient temperature reaction 1.5h in dispersion liquid.Product is through washing, drying in the baking oven of 70 DEG C, and obtaining specific area is 460m
2g
-1, composite material diameter to be 140 ~ 300nm and nitrogen mass percentage be 3% manganese dioxide/nitrating carbon fiber anode material.
Take a certain amount of above-mentioned obtained manganese dioxide/nitrating carbon fiber negative material, add 20% conductive black as conductive agent, 10% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1M NaClO4/EC:DEC (1:1)+5wt%FEC, and test charging and discharging currents density is 500mA/g.
The sode cell electrode adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 100 circle specific capacity still can remain on 336.4mA h/g; Show good cycle performance.High rate performance under different discharge-rate is bent, and can find that this composite material has excellent high rate performance, after current density slowly gets back to small area analysis 500mA/g by big current 2000mA/g, capacity is returned to again 330.4mA h/g.
Embodiment 3
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business, blending bacteria cellulose film makes it form uniform suspension-turbid liquid, get 100mL bacteria cellulose suspension-turbid liquid and add 50mL sal volatile (0.05mol/L) and 50mL urea liquid (0.05mol/L) stirring reaction 12h, after filtering and washing, at-30 DEG C of temperature, freeze drying example 30h obtains nitrating bacteria cellulose.Be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, temperature risen to 500 DEG C, after insulation 3h, obtain nitrating carbon fiber.With the 100mL concentrated sulfuric acid and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidification 12h nitrating carbon fibers, product is through washing, drying, obtain the nitrating carbon fiber of acidification, getting the nitrating carbon fiber after 0.1g acidification is dispersed in the deionized water of 150mL, ultrasonic 60min obtains uniform dispersion liquid, 0.2g sodium permanganate and 0.18g manganese sulfate is added again, stirred at ambient temperature reaction 1h in dispersion liquid.Product is through washing, drying in the baking oven of 80 DEG C, and obtaining specific area is 500m
2g
-1, composite material diameter to be 100 ~ 200nm and nitrogen mass percentage be 4.5% manganese dioxide/nitrating carbon fiber anode material.
Take a certain amount of above-mentioned obtained manganese dioxide/nitrating carbon fiber negative material, add 20% conductive black as conductive agent, 10% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1M NaClO
4/ EC:DEC (1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
The sode cell electrode adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 100 circle specific capacity still can remain on 340.1mA h/g; Show good cycle performance.High rate performance under different discharge-rate is bent, and can find that this composite material has excellent high rate performance, after current density slowly gets back to small area analysis 500mA/g by big current 2000mA/g, capacity is returned to again 330.2mA h/g.
Embodiment 4
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business, blending bacteria cellulose film makes it form uniform suspension-turbid liquid, get 100mL bacteria cellulose suspension-turbid liquid and add 50mL ammonium chloride solution (0.02mol/L) and 50mL urea liquid (0.02mol/L) stirring reaction 24h, after filtering and washing, at-48 DEG C of temperature, freeze drying example 28h obtains nitrating bacteria cellulose.Be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, temperature risen to 600 DEG C, after insulation 2h, obtain nitrating carbon fiber.With the 100mL concentrated sulfuric acid and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidification 10h nitrating carbon fibers, product is through washing, drying, obtain the nitrating carbon fiber of acidification, getting the nitrating carbon fiber after 0.2g acidification is dispersed in the deionized water of 300mL, ultrasonic 40min obtains uniform dispersion liquid, 0.3g potassium permanganate and 0.27g manganese sulfate is added again, stirred at ambient temperature reaction 2h in dispersion liquid.Product is through washing, drying in the baking oven of 90 DEG C, and obtaining specific area is 300m
2g
-1, composite material diameter to be 110 ~ 280nm and nitrogen mass percentage be 2.6% manganese dioxide/nitrating carbon fiber anode material.
Take a certain amount of above-mentioned obtained manganese dioxide/nitrating carbon fiber negative material, add 20% conductive black as conductive agent, 10% sodium alginate is as binding agent, add a small amount of water and be thoroughly mixed to form uniform pastel through grinding, be coated on Copper Foil matrix as test electrode, make button cell using sodium metal as to electrode, its electrolyte is 1M NaClO
4/ EC:DEC (1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
The sode cell electrode adopting the present embodiment to prepare and sodium sheet are assembled into button cell, and at room temperature when 500mA/g constant-current discharge, circulation 100 circle specific capacity still can remain on 334.3mA h/g; Show good cycle performance.High rate performance under different discharge-rate is bent, and can find that this composite material has excellent high rate performance, after current density slowly gets back to small area analysis 500mA/g by big current 2000mA/g, capacity is returned to again 329.5.mA h/g.
Comparative example 1
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business, blending bacteria cellulose film makes it form uniform suspension-turbid liquid, get 100mL bacteria cellulose suspension-turbid liquid and add 50mL ammonium chloride solution (0.1mol/L) and 50mL urea liquid (0.1mol/L) stirring reaction 24h, after filtering and washing, at-48 DEG C of temperature, freeze drying example 12h obtains nitrating bacteria cellulose.Be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, temperature risen to 500 DEG C, after insulation 3h, obtain nitrating carbon fiber.With the 100mL concentrated sulfuric acid and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidification 10h nitrating carbon fibers, product is through washing, drying, obtain the nitrating carbon fiber of acidification, getting the nitrating carbon fiber after 0.1g acidification is dispersed in the deionized water of 150mL, ultrasonic 30min obtains uniform dispersion liquid, 0.3g potassium permanganate and 0.27g sodium sulphate is added again, stirred at ambient temperature reaction 8h in dispersion liquid.Product, through washing, drying in the baking oven of 90 DEG C, obtains manganese dioxide/nitrating carbon fiber anode material.
Fig. 2 adopts the present embodiment to obtain the SEM figure of manganese dioxide/nitrating carbon fibre composite, and as can be seen from the figure, because reaction time long manganese dioxide does not have homoepitaxial at nitrating carbon fiber surface, but caking mixes with nitrating carbon fiber.
Comparative example 2
With the bacteria cellulose film (being kept in refrigerator) of a large amount of washed with de-ionized water business; blending bacteria cellulose film makes it form uniform suspension-turbid liquid; after filtering and washing; freeze drying example 24h at-50 DEG C of temperature; be placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 3 DEG C/min; temperature is risen to 600 DEG C, after insulation 3h, obtain carbon fiber.Getting 0.15g carbon fiber is dispersed in the deionized water of 200mL, and ultrasonic 40min obtains uniform dispersion liquid, then in dispersion liquid, add 0.4g potassium permanganate and 0.36g manganese sulfate, stirred at ambient temperature reaction 1h.Product, through washing, drying in the baking oven of 80 DEG C, obtains manganese dioxide/nitrating carbon fiber anode material.
Fig. 3 adopt the present embodiment be manganese dioxide/carbon fibrous composite SEM figure.The present embodiment does not carry out nitrating process and acidification to material with carbon element, in the manganese dioxide/carbon fibrous composite obtained by the method, carbon fiber surface is comparatively smooth, material diameter is 40 ~ 100nm, less than the diameter of the composite material in Fig. 1, and manganese dioxide does not have homoepitaxial at carbon fiber surface, a small amount of block manganese dioxide is long at carbon fiber surface dispersedly.
Claims (10)
1. the manganese dioxide for sodium-ion battery/nitrating carbon fiber anode material, it is characterized in that, this composite material is the anode material of the even coated nitrating carbon fiber of manganese dioxide, and preparation method, for be blended by bacteria cellulose film, forms uniform suspension-turbid liquid; The mixed solution of ammonium salt solution and urea liquid is added in bacteria cellulose suspension-turbid liquid, stirring reaction, after freeze drying, heat treatment obtains nitrating carbon fiber, acidification nitrating carbon fiber, and it is in aqueous dispersed, add permanganate and sulfate again, stirred at ambient temperature reacts, and after washing drying, obtains manganese dioxide/nitrating carbon fiber anode material.
2. manganese dioxide according to claim 1/nitrating carbon fiber anode material, it is characterized in that, sublimation drying is 25 ~ 30h, and the stirring reaction time adding potassium permanganate and sodium sulphate is 1 ~ 5h.
3. manganese dioxide according to claim 1/nitrating carbon fiber anode material, is characterized in that, described ammonium salt is selected from one or more in ammonium chloride, ammonium sulfate, ammonium carbonate or carbonic hydroammonium, and the concentration of ammonium salt solution is 0.01 ~ 0.1mol/L; The concentration of urea liquid is 0.01 ~ 0.1mol/L, and the volume ratio of ammonium salt solution and urea liquid is 1 ~ 3:1.
4. manganese dioxide according to claim 1/nitrating carbon fiber anode material, is characterized in that, the method for acidification is that nitrating carbon fiber to be dispersed in volume ratio be in the concentrated sulfuric acid of 1:1 ~ 3 and the solution of red fuming nitric acid (RFNA), stirring reaction 8 ~ 12h.
5. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, is characterized in that, the diameter of manganese dioxide/nitrating carbon fiber anode material is 100 ~ 400nm.
6. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, is characterized in that, the specific area of described manganese dioxide/nitrating carbon fibre composite is 100 ~ 700m
2g
-1, in composite material, nitrogen content is 2 ~ 10wt%.
7. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, is characterized in that, the quality of manganese dioxide accounts for 50 ~ 90% of manganese dioxide/nitrating carbon fiber gross mass.
8. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, is characterized in that, the mol ratio of permanganate and sulfate is 1:1 ~ 4, and the mass ratio of nitrating carbon fiber and permanganate is 1:1 ~ 4; Described permanganate be selected from potassium permanganate or sodium permanganate one or both, described sulfate be selected from sodium sulphate or manganese sulfate one or both.
9. the preparation method of the manganese dioxide described in any one of claim 1-8/nitrating carbon fiber anode material, is characterized in that, preparation method, for be blended by bacteria cellulose film, makes it form uniform suspension-turbid liquid; In bacteria cellulose suspension-turbid liquid, add the mixed solution of ammonium salt solution and urea liquid, stirring reaction, after freeze drying, heat treatment obtains nitrating carbon fiber; Acidification nitrating carbon fiber, it is in aqueous dispersed, then add permanganate and sulfate, stirred at ambient temperature reacts, and after washing drying, obtains manganese dioxide/nitrating carbon fiber anode material.
10. the preparation method of manganese dioxide according to claim 9/nitrating carbon fiber anode material, it is characterized in that, bacteria cellulose film is blended, it is made to form uniform suspension-turbid liquid, the mixed solution of ammonium salt solution and urea liquid is added in suspension-turbid liquid, stirring reaction 10 ~ 24h, product through 25 ~ 30h freeze drying, obtains nitrating bacteria cellulose at-20 ~-60 DEG C; Under inert atmosphere protection, with the heating rate of 1 ~ 10 DEG C/min, temperature is risen to 500 ~ 800 DEG C, after insulation 2 ~ 10h, obtain nitrating carbon fiber; After the concentrated sulfuric acid and concentrated nitric acid solution acidification nitrating carbon fiber, then joined deionized water for ultrasonic dispersion and obtained dispersion liquid, in dispersion liquid, added permanganate and sulfate and after fully dissolving, stirring at room temperature reaction 1 ~ 5h; Product, after washing, 60 ~ 90 DEG C of dryings, obtains manganese dioxide/nitrating carbon fiber anode material.
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| CN105778497A (en) * | 2016-04-25 | 2016-07-20 | 南京理工大学 | Bacterial cellulose/manganese dioxide/polypyrrole composite film and preparation method thereof |
| CN106098412A (en) * | 2016-06-29 | 2016-11-09 | 广西桂柳化工有限责任公司 | The preparation method of indium nitrate dopping manganese dioxide ultra-capacitor electrode material |
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| CN108448051A (en) * | 2018-04-11 | 2018-08-24 | 深圳市源驰科技有限公司 | Water system sodium-ion battery Na0.58Mn2O4·1.38H2O materials and the preparation method and application thereof, electrode |
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| CN115714167A (en) * | 2022-11-07 | 2023-02-24 | 武汉理工大学 | Manganese dioxide chemically modified carbon fluoride material, and preparation method and application thereof |
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| CN101320809A (en) * | 2008-07-17 | 2008-12-10 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101320809A (en) * | 2008-07-17 | 2008-12-10 | 深圳市贝特瑞新能源材料股份有限公司 | Lithium ion battery anode material manganese lithium phosphate and preparation method thereof |
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| CN105778497B (en) * | 2016-04-25 | 2017-12-08 | 南京理工大学 | A kind of bacteria cellulose/manganese dioxide/composite polypyrrole film and preparation method thereof |
| CN105778497A (en) * | 2016-04-25 | 2016-07-20 | 南京理工大学 | Bacterial cellulose/manganese dioxide/polypyrrole composite film and preparation method thereof |
| CN106098412A (en) * | 2016-06-29 | 2016-11-09 | 广西桂柳化工有限责任公司 | The preparation method of indium nitrate dopping manganese dioxide ultra-capacitor electrode material |
| CN107785589A (en) * | 2017-10-12 | 2018-03-09 | 太原科技大学 | A kind of preparation method of iron cobalt compound@bacteria cellulose lithium air battery positive electrode materials |
| CN107978741A (en) * | 2017-11-17 | 2018-05-01 | 中南大学 | A kind of preparation method of lithium-sulfur cell anode composite material |
| CN107978741B (en) * | 2017-11-17 | 2020-09-01 | 中南大学 | Preparation method of positive electrode composite material for lithium-sulfur battery |
| CN108630916B (en) * | 2018-03-28 | 2021-02-12 | 浙江大学 | Bacterial cellulose-loaded titanium niobium oxygen composite material and preparation method and application thereof |
| CN108630916A (en) * | 2018-03-28 | 2018-10-09 | 浙江大学 | A kind of bacteria cellulose supported titanium niobium O compoiste material and its preparation method and application |
| CN108448051A (en) * | 2018-04-11 | 2018-08-24 | 深圳市源驰科技有限公司 | Water system sodium-ion battery Na0.58Mn2O4·1.38H2O materials and the preparation method and application thereof, electrode |
| CN108922790A (en) * | 2018-07-11 | 2018-11-30 | 黑龙江科技大学 | A kind of manganese dioxide/N doping porous carbon composite preparation method and application of sodium ion insertion |
| CN108922790B (en) * | 2018-07-11 | 2020-04-21 | 黑龙江科技大学 | Preparation method and application of composite material |
| CN110719891A (en) * | 2018-11-23 | 2020-01-21 | 辽宁星空钠电电池有限公司 | Biomass-based hard carbon negative electrode material of sodium ion battery and preparation method and application thereof |
| CN112520722A (en) * | 2020-12-02 | 2021-03-19 | 深圳大学 | Titanium dioxide coated biomass charcoal composite anode material and preparation method and application thereof |
| CN113193178A (en) * | 2020-12-07 | 2021-07-30 | 北京服装学院 | Preparation method of manganese dioxide nanosheet coated carbon fiber for supplying power to intelligent clothes |
| CN113213543A (en) * | 2021-05-13 | 2021-08-06 | 陕西科技大学 | MnO (MnO)2/V2O3Process for preparing nano composite material |
| CN115714167A (en) * | 2022-11-07 | 2023-02-24 | 武汉理工大学 | Manganese dioxide chemically modified carbon fluoride material, and preparation method and application thereof |
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