CN104993111B - 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, and in particular to a kind of manganese dioxide/nitrating carbon for sodium-ion battery
Fiber negative material and preparation method thereof.
Background technology
Between over the past thirty years, the battery of lithium ion is fast-developing so as to dominated the shifting such as PC, video camera, mobile phone
Dynamic device battery market.And with the good application prospect of electric motor car, hybrid vehicle aspect, the demand of lithium battery is continuous
Increase, is limited by lithium price, storage capacity, and lithium ion battery has developed into bottleneck period.Sode cell is due to resource reserves
Abundant, low cost receives extensive concern, and the research and development of sodium-ion battery can be relaxed to a certain extent because of lithium resource shortage
The battery development limitation problem of initiation.Yet with sodium ion ionic radius (0.102nm) than the ionic radius of lithium ion
(0.76nm) it is much larger so that sodium ion is embedded in more difficult than lithium ion with abjection in battery material.Some are such as Graphene
Be not particularly suited for sodium-ion battery etc. the electrode material of preferable lithium ion battery, and the research of sodium-ion battery also it
Its development early stage.Thus, exploitation excellent performance, cheap sodium-ion battery positive and negative pole material are particularly important.This
It is a research emphasis from now on, is a significant challenge of current sodium-ion battery development.
Manganese dioxide (MnO2) be a kind of important VIIB-VIA compound semiconductors, as one kind have different crystal forms,
Rich content, environmental friendliness and chemically stable material, obtain extensively in fields such as electrolytic lead zinc, glass, ceramics, medicine and batteries
General application, but manganese dioxide is as sodium cell negative pole material, and then rare people reports.Research discovery, MnO2Also there is very high reason
By storage sodium specific capacity, but because itself electrons/ions electrical conductivity is very low, and exist during deintercalation sodium serious
Volumetric expansion, causes its cyclical stability extremely low.
The content of the invention
The defect that the present invention exists for existing sodium-ion battery material, there is provided a kind of low cost, manganese dioxide is uniform
Be grown in nitrating carbon fiber surface, for be obtained in that in sodium-ion battery high charge-discharge specific capacity, good high rate performance and
The manganese dioxide of cycle performance/nitrating carbon fiber anode material.
It is to provide a kind of process is simple, reproducible, with low cost, eco-friendly that another object of the present invention is
The preparation method of above-mentioned composite.
Technical scheme：
The invention provides a kind of anode material of the manganese dioxide/nitrating carbon fiber for sodium-ion battery, should
Composite is the anode material that manganese dioxide uniformly coats nitrating carbon fiber, and preparation method is to stir bacteria cellulose film
It is broken so as to form uniform suspension；The mixed solution of ammonium salt solution and urea liquid is added in bacteria cellulose suspension,
Stirring reaction, after freeze-drying, is thermally treated resulting in nitrating carbon fiber；Acidification nitrating carbon fiber, is dispersed in water
In solution, permanganate and sulfate are added, stirring reaction under room temperature after washing is dried, obtains final product manganese dioxide/nitrating carbon fine
Dimension anode material.
The diameter of manganese dioxide/nitrating carbon fiber anode material is preferably 100～400nm.
Manganese dioxide/nitrating carbon fiber anode material specific surface area is preferably 100～700m2g-1。
Nitrogen content is preferably 2～10wt% in manganese dioxide/nitrating carbon fiber anode material.
It is preferred that the quality of manganese dioxide accounts for manganese dioxide and nitrating carbon in manganese dioxide/nitrating carbon fiber anode material
The 50～90% of total fiber mass.
Present invention also offers a kind of anode material of the manganese dioxide/nitrating carbon fiber for sodium-ion battery
Preparation method, preparation method is to blend bacteria cellulose film so as to form uniform suspension；To bacteria cellulose suspension
The mixed solution of middle addition ammonium salt solution and urea liquid, stirring reaction after freeze-drying, is thermally treated resulting in nitrating carbon fiber；
Acidification nitrating carbon fiber, its is dispersed in aqueous, permanganate and sulfate are added, stir anti-under room temperature
Should, after washing is dried, obtain final product manganese dioxide/nitrating carbon fiber anode material.
Preferred preparation method is：Bacteria cellulose film is blended so as to form uniform suspension, added in suspension
Enter the mixed solution of ammonium salt solution and urea liquid, 10～24h of stirring reaction, product is freezed in -20～-60 DEG C of 25～30h of Jing
It is dried, obtains nitrating bacteria cellulose；Under inert atmosphere protection, with the heating rate of 1～10 DEG C/min, temperature is risen to
500～800 DEG C, after 2～10h of insulation nitrating carbon fiber is obtained；With the concentrated sulfuric acid and concentrated nitric acid solution acidification nitrating carbon fiber
Afterwards, then add it to ultrasonic disperse in deionized water and obtain dispersion liquid, permanganate and sulfate are added simultaneously in dispersion liquid
Fully after dissolving, 1～5h of reaction is stirred at room temperature；Product is scrubbed, after 60～90 DEG C of dryings, obtain manganese dioxide/nitrating
Carbon fiber anode material.
In above-mentioned preparation method, further preferred sublimation drying is 25～30h.
Potassium permanganate and the stirring reaction time of sodium sulphate is added to be preferably 1～5h.
Described ammonium salt is preferably selected from one or more in ammonium chloride, ammonium sulfate, ammonium carbonate or ammonium hydrogen carbonate.
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 that nitrating carbon fiber is dispersed in into volume ratio to be preferably 1:1～3 concentrated sulfuric acid and red fuming nitric acid (RFNA)
Solution in.
The stirring reaction time of acidification is preferably 8～12h.
It is preferred that the mol ratio of permanganate and sulfate is 1:1～4.
Nitrating carbon fiber is preferably 1 with the mass ratio of permanganate:1～4.
Described permanganate is preferably selected from one or two in potassium permanganate or sodium permanganate.
Described sulfate is preferably selected from one or two in sodium sulphate or manganese sulfate.
Beneficial effects of the present invention：
The invention provides a kind of manganese dioxide homoepitaxial is in nitrating carbon fiber surface, for can in sodium-ion battery
Obtain the manganese dioxide/nitrating carbon fiber anode material of high charge-discharge specific capacity, good high rate performance and long circulation life.
Nitrating carbon fiber in the present invention has the network structure being connected with each other, and manganese dioxide homoepitaxial, should on nitrating carbon fiber
Structure also can be maintained, and nitrating carbon fiber provides effective conductive network for sodium-ion battery and sodium ion migration is logical
Road, it is ensured that good ion transport capability, is applied in sodium ion show excellent performance.The present invention by doping nitrogen with
And acidification carbon fiber, make carbon fiber surface that there is abundant functional group, further ensure that manganese dioxide in carbon fiber surface
The homoepitaxial in face and more preferable chemical property.Additionally, the manganese dioxide of the present invention/nitrating carbon fiber anode material
Preparation method it is simple, reproducible, with low cost, environmental friendliness is adapted to industrialized production.The dioxy that the method is prepared
Change the negative composite of manganese/nitrating carbon fiber, during as anode material of lithium-ion battery, with very high charging and discharging capacity and good
Good cycle performance.
Description of the drawings
【Fig. 1】For the scanning electron microscope (SEM) photograph (SEM) of manganese dioxide in embodiment 1/nitrating carbon fibre composite.
【Fig. 2】For the scanning electron microscope (SEM) photograph (SEM) of manganese dioxide in comparative example 1/nitrating carbon fibre composite.
【Fig. 3】For the scanning electron microscope (SEM) photograph (SEM) of manganese dioxide/Carbon Nanofibers/Epoxy Resin Composite Materials in comparative example 2.
【Fig. 4】For the x-ray diffraction figure (XRD) of manganese dioxide in embodiment 1/nitrating carbon fibre composite.
【Fig. 5】The sodium-ion battery of manganese dioxide/nitrating carbon fiber anode material assembling obtained in embodiment 1
100 cyclic discharge capacity curve maps.
【Fig. 6】The sodium-ion battery of manganese dioxide/nitrating carbon fiber anode material assembling obtained in embodiment 1
High rate performance figure.
Specific embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, takes 100mL bacteria celluloses suspension and adds 50mL ammonium chloride solutions (0.1mol/L) and 50mL
Urea liquid (0.1mol/L) stirring reaction 20h, Jing after filtering and washing, freeze drying example 25h is mixed at a temperature of -48 DEG C
Azotobacter cellulose.It is placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, by temperature liter
To 600 DEG C, after insulation 2h nitrating carbon fiber is obtained.With the 100mL concentrated sulfuric acids and concentrated nitric acid solution (volume ratio 1:3) at 80 DEG C of acidifyings
Reason 10h nitrating carbon fibers, product is scrubbed, dry, the nitrating carbon fiber of acidification is obtained, after taking 0.1g acidifications
Nitrating carbon fiber be dispersed in the deionized water of 150mL, ultrasonic 40min obtains uniform dispersion liquid, then in dispersion liquid plus
Enter 0.3g potassium permanganate and 0.27g sodium sulphate, stirring reaction 1h under room temperature.Product is scrubbed, dry in 80 DEG C of baking oven
It is dry, specific surface area is obtained for 600m2g-1, a diameter of 100～270nm of composite and the dioxy that nitrogen weight/mass percentage composition is 6%
Change manganese/nitrating carbon fiber anode material.
A certain amount of manganese dioxide obtained above/nitrating carbon fiber negative material is weighed, adds 10% conductive black to make
For conductive agent, 10% sodium alginate as binding agent, plus it is a small amount of water is ground is thoroughly mixed to form uniform pastel, be coated in
As test electrode on Copper Foil matrix, button cell is made as to electrode using metallic sodium, its electrolyte is 1M NaClO4/EC:
DEC(1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
Button cell is assembled into using sode cell electrode manufactured in the present embodiment and sodium piece, its chemical property such as Fig. 5～6
It is shown：
Manganese dioxide homoepitaxial is can be seen that in Fig. 1 in nitrating carbon fiber surface, composite is connected with each other in presentation
Network structure, a diameter of 100～270nm of composite.
Can be seen that in Fig. 4 in manganese dioxide/nitrating carbon fiber negative material the position of each diffraction maximum and relative intensity with
JCPDS (JCPDS) card (80-1098) matches, and shows that product is rhombic MnO2。
Show in Fig. 5 using manganese dioxide/electrode made by nitrating carbon fiber negative material, at room temperature in 500mA/g
During constant-current discharge, circulation 100 is enclosed specific capacity and may remain in 355mA h/g；Show good cycle performance.
Show in Fig. 6 using manganese dioxide/electrode respective battery made by nitrating carbon fiber negative material in different electric discharges
High rate performance under multiplying power is bent, it can be found that the composite has excellent high rate performance, under big multiplying power 2000mA/g, holds
Amount may remain in 314mA h/g, and capacity is returned to 346.1mA again after current density slowly returns to 500mA/g by high current
h/g。
Embodiment 2
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, take 100mL bacteria celluloses suspension add 100mL ammonium sulfates (0.05mol/L) and
50mL urea liquids (0.05mol/L) stirring reaction 18h, Jing after filtering and washing, the freeze drying example 30h at a temperature of -50 DEG C
Obtain nitrating bacteria cellulose.It is placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 3 DEG C/min, will
Temperature rises to 500 DEG C, and after insulation 3h nitrating carbon fiber is obtained.With the 100mL concentrated sulfuric acids and concentrated nitric acid solution (volume ratio 1:3)80℃
Acidification 8h nitrating carbon fiber, product is scrubbed, dry, obtains the nitrating carbon fiber of acidification, takes 0.15g acidifyings
Nitrating carbon fiber after process is dispersed in the deionized water of 250mL, and ultrasonic 60min obtains uniform dispersion liquid, then in dispersion
0.45g potassium permanganate and 0.4g sodium sulphate, stirring reaction 1.5h under room temperature are added in liquid.Product is scrubbed, at 70 DEG C
It is dried in baking oven, obtains specific surface area for 460m2g-1, a diameter of 140～300nm of composite and nitrogen weight/mass percentage composition are
3% manganese dioxide/nitrating carbon fiber anode material.
A certain amount of manganese dioxide obtained above/nitrating carbon fiber negative material is weighed, adds 20% conductive black to make
For conductive agent, 10% sodium alginate as binding agent, plus it is a small amount of water is ground is thoroughly mixed to form uniform pastel, be coated in
As test electrode on Copper Foil matrix, button cell is made as to electrode using metallic sodium, its electrolyte is 1M NaClO4/EC:
DEC(1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
Button cell is assembled into using sode cell electrode manufactured in the present embodiment and sodium piece, it is permanent in 500mA/g at room temperature
When banishing electricity, circulation 100 is enclosed specific capacity and may remain in 336.4mA h/g；Show good cycle performance.In different electric discharges
High rate performance under multiplying power is bent, it can be found that the composite has excellent high rate performance, when current density is by high current
2000mA/g slowly returns to capacity after small current 500mA/g and is returned to 330.4mA h/g again.
Embodiment 3
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, takes 100mL bacteria celluloses suspension and adds 50mL sal volatiles (0.05mol/L) and 50mL
Urea liquid (0.05mol/L) stirring reaction 12h, Jing after filtering and washing, freeze drying example 30h is obtained at a temperature of -30 DEG C
Nitrating bacteria cellulose.It is placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, by temperature
500 DEG C are risen to, after insulation 3h nitrating carbon fiber is obtained.With the 100mL concentrated sulfuric acids and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidifyings
12h nitrating carbon fibers are processed, product is scrubbed, dry, obtains the nitrating carbon fiber of acidification, takes 0.1g acidifications
Nitrating carbon fiber afterwards is dispersed in the deionized water of 150mL, and ultrasonic 60min obtains uniform dispersion liquid, then in dispersion liquid
Add 0.2g sodium permanganates and 0.18g manganese sulfates, stirring reaction 1h under room temperature.Product is scrubbed, in 80 DEG C of baking oven
It is dried, obtains specific surface area for 500m2g-1, a diameter of 100～200nm of composite and nitrogen weight/mass percentage composition are 4.5%
Manganese dioxide/nitrating carbon fiber anode material.
A certain amount of manganese dioxide obtained above/nitrating carbon fiber negative material is weighed, adds 20% conductive black to make
For conductive agent, 10% sodium alginate as binding agent, plus it is a small amount of water is ground is thoroughly mixed to form uniform pastel, be coated in
As test electrode on Copper Foil matrix, button cell is made as to electrode using metallic sodium, its electrolyte is 1M NaClO4/EC:
DEC(1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
Button cell is assembled into using sode cell electrode manufactured in the present embodiment and sodium piece, it is permanent in 500mA/g at room temperature
When banishing electricity, circulation 100 is enclosed specific capacity and may remain in 340.1mA h/g；Show good cycle performance.In different electric discharges
High rate performance under multiplying power is bent, it can be found that the composite has excellent high rate performance, when current density is by high current
2000mA/g slowly returns to capacity after small current 500mA/g and is returned to 330.2mA h/g again.
Embodiment 4
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, takes 100mL bacteria celluloses suspension and adds 50mL ammonium chloride solutions (0.02mol/L) and 50mL
Urea liquid (0.02mol/L) stirring reaction 24h, Jing after filtering and washing, freeze drying example 28h is obtained at a temperature of -48 DEG C
Nitrating bacteria cellulose.It is placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, by temperature
600 DEG C are risen to, after insulation 2h nitrating carbon fiber is obtained.With the 100mL concentrated sulfuric acids and concentrated nitric acid solution (volume ratio 1:3) 80 DEG C of acidifyings
10h nitrating carbon fibers are processed, product is scrubbed, dry, obtains the nitrating carbon fiber of acidification, takes 0.2g acidifications
Nitrating carbon fiber afterwards is dispersed in the deionized water of 300mL, and ultrasonic 40min obtains uniform dispersion liquid, then in dispersion liquid
Add 0.3g potassium permanganate and 0.27g manganese sulfates, stirring reaction 2h under room temperature.Product is scrubbed, in 90 DEG C of baking oven
It is dried, obtains specific surface area for 300m2g-1, a diameter of 110～280nm of composite and nitrogen weight/mass percentage composition are 2.6%
Manganese dioxide/nitrating carbon fiber anode material.
A certain amount of manganese dioxide obtained above/nitrating carbon fiber negative material is weighed, adds 20% conductive black to make
For conductive agent, 10% sodium alginate as binding agent, plus it is a small amount of water is ground is thoroughly mixed to form uniform pastel, be coated in
As test electrode on Copper Foil matrix, button cell is made as to electrode using metallic sodium, its electrolyte is 1M NaClO4/EC:
DEC(1:1)+5wt%FEC, test charging and discharging currents density is 500mA/g.
Button cell is assembled into using sode cell electrode manufactured in the present embodiment and sodium piece, it is permanent in 500mA/g at room temperature
When banishing electricity, circulation 100 is enclosed specific capacity and may remain in 334.3mA h/g；Show good cycle performance.In different electric discharges
High rate performance under multiplying power is bent, it can be found that the composite has excellent high rate performance, when current density is by high current
2000mA/g slowly returns to capacity after small current 500mA/g and is returned to 329.5.mA h/g again.
Comparative example 1
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, takes 100mL bacteria celluloses suspension and adds 50mL ammonium chloride solutions (0.1mol/L) and 50mL
Urea liquid (0.1mol/L) stirring reaction 24h, Jing after filtering and washing, freeze drying example 12h is mixed at a temperature of -48 DEG C
Azotobacter cellulose.It is placed on again in tube furnace, under inert atmosphere protection, with the heating rate of 5 DEG C/min, by temperature liter
To 500 DEG C, after insulation 3h nitrating carbon fiber is obtained.With the 100mL concentrated sulfuric acids and concentrated nitric acid solution (volume ratio 1:3) at 80 DEG C of acidifyings
Reason 10h nitrating carbon fibers, product is scrubbed, dry, the nitrating carbon fiber of acidification is obtained, after taking 0.1g acidifications
Nitrating carbon fiber be dispersed in the deionized water of 150mL, ultrasonic 30min obtains uniform dispersion liquid, then in dispersion liquid plus
Enter 0.3g potassium permanganate and 0.27g sodium sulphate, stirring reaction 8h under room temperature.Product is scrubbed, dry in 90 DEG C of baking oven
It is dry, obtain manganese dioxide/nitrating carbon fiber anode material.
Fig. 2 obtains the SEM figures of manganese dioxide/nitrating carbon fibre composite using the present embodiment, it can be seen that
Because reaction time long manganese dioxide does not have homoepitaxial in nitrating carbon fiber surface, but caking is mixed with nitrating carbon fiber
Close.
Comparative example 2
The bacteria cellulose film (being stored in refrigerator) of business is cleaned with a large amount of deionized waters, blending bacteria cellulose film makes
It forms uniform suspension, Jing after filtering and washing, the freeze drying example 24h at a temperature of -50 DEG C, then it is placed on tube furnace
In, under inert atmosphere protection, with the heating rate of 3 DEG C/min, temperature is risen to into 600 DEG C, obtain carbon fiber after insulation 3h.Take
0.15g carbon fibers are dispersed in the deionized water of 200mL, and ultrasonic 40min obtains uniform dispersion liquid, then adds in dispersion liquid
0.4g potassium permanganate and 0.36g manganese sulfates, stirring reaction 1h under room temperature.Product is scrubbed, dry in 80 DEG C of baking oven,
Obtain manganese dioxide/nitrating carbon fiber anode material.
Fig. 3 adopts the present embodiment to scheme for the SEM of manganese dioxide/carbon fibrous composite.The present embodiment is not to material with carbon element
Nitrating process and acidification are carried out, in the manganese dioxide/carbon fibrous composite obtained with the method, carbon fiber surface is more
Smooth, material diameter is 40～100nm, less than the diameter of the composite in Fig. 1, and manganese dioxide does not have homoepitaxial in carbon
Fiber surface, a small amount of block manganese dioxide is dispersedly grown in carbon fiber surface.
Claims (10)
1. a kind of manganese dioxide/nitrating carbon fiber anode material for sodium-ion battery, it is characterised in that the composite wood
Material is the anode material that manganese dioxide uniformly coats nitrating carbon fiber, and preparation method is to blend bacteria cellulose film, shape
Uniformly suspension；The mixed solution of addition ammonium salt solution and urea liquid in bacteria cellulose suspension, stirring reaction,
After freeze-drying, nitrating carbon fiber is thermally treated resulting in, acidification nitrating carbon fiber is dispersed in aqueous by its, then
Permanganate and sulfate, stirring reaction under room temperature is added after washing is dried, to obtain final product manganese dioxide/nitrating carbon fiber negative pole and answer
Condensation material.
2. manganese dioxide according to claim 1/nitrating carbon fiber anode material, it is characterised in that freeze-drying
Time is 25～30h, and the stirring reaction time for adding potassium permanganate and sodium sulphate is 1～5h.
3. manganese dioxide according to claim 1/nitrating carbon fiber anode material, it is characterised in that described ammonium
Salt in ammonium chloride, ammonium sulfate, ammonium carbonate or the ammonium hydrogen carbonate one or more, the concentration of ammonium salt solution is 0.01～
0.1mol/L；The concentration of urea liquid is 1～3 for the volume ratio of 0.01～0.1mol/L, ammonium salt solution and urea liquid:1.
4. manganese dioxide according to claim 1/nitrating carbon fiber anode material, it is characterised in that acidification
Method be that nitrating carbon fiber is dispersed in into volume ratio for 1:In 1～3 concentrated sulfuric acid 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, it is characterised in that
A diameter of 100～400nm of manganese dioxide/nitrating carbon fiber anode material.
6. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, it is characterised in that
The specific surface area of described manganese dioxide/nitrating carbon fibre composite is 100～700m2g-1, nitrogen content is 2 in composite
～10wt%.
7. the manganese dioxide according to any one of claim 1-4/nitrating carbon fiber anode material, it is characterised in that
The quality of manganese dioxide accounts for the 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, it is characterised in that
The mol ratio of permanganate and sulfate is 1:1～4, nitrating carbon fiber is 1 with the mass ratio of permanganate:1～4；Described
One or two in potassium permanganate or sodium permanganate of permanganate, described sulfate is in sodium sulphate or manganese sulfate
One or two.
9. the preparation method of the manganese dioxide described in any one of claim 1-8/nitrating carbon fiber anode material, its feature
It is that preparation method is to blend bacteria cellulose film so as to form uniform suspension；Add in bacteria cellulose suspension
Enter the mixed solution of ammonium salt solution and urea liquid, stirring reaction after freeze-drying, is thermally treated resulting in nitrating carbon fiber；Acidifying
Nitrating carbon fiber is processed, its is dispersed in aqueous, permanganate and sulfate are added, stirring reaction under room temperature,
After washing is dried, manganese dioxide/nitrating carbon fiber anode material is obtained final product.
10. the preparation method of the manganese dioxide described in claim 9/nitrating carbon fiber anode material, it is characterised in that will
Bacteria cellulose film is blended so as to form uniform suspension, and the mixing of ammonium salt solution and urea liquid is added in suspension
Solution, 10～24h of stirring reaction, product obtains nitrating bacteria cellulose in -20～-60 DEG C of Jing 25～30h freeze-dryings；
Under inert atmosphere protection, with the heating rate of 1～10 DEG C/min, temperature is risen to into 500～800 DEG C, obtained after 2～10h of insulation
Nitrating carbon fiber；After with the concentrated sulfuric acid and concentrated nitric acid solution acidification nitrating carbon fiber, then add it to surpass in deionized water
Sound dispersion obtains dispersion liquid, permanganate and sulfate is added in dispersion liquid and fully after dissolving, be stirred at room temperature reaction 1～
5h；Product is scrubbed, after 60～90 DEG C of dryings, obtain manganese dioxide/nitrating carbon fiber anode material.
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| CN201510323596.3A CN104993111B (en) | 2015-06-12 | 2015-06-12 | Manganese dioxide/nitrating carbon fiber cathode composite material for sodium-ion battery and preparing method thereof |
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| 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 |
| 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 |
| CN108448051B (en) * | 2018-04-11 | 2020-11-03 | 深圳市源驰科技有限公司 | Aqueous sodium ion battery Na0.58Mn2O4·1.38H2O material, preparation method and application thereof, and electrode |
| 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 |
| CN112520722B (en) * | 2020-12-02 | 2022-11-22 | 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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