CN106356517A - Plant biomass carbon doped sulfur-nitrogen composite material of cathode of sodium ion battery and lithium ion battery and preparation method of plant biomass carbon doped sulfur-nitrogen composite material - Google Patents
Plant biomass carbon doped sulfur-nitrogen composite material of cathode of sodium ion battery and lithium ion battery and preparation method of plant biomass carbon doped sulfur-nitrogen composite material Download PDFInfo
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- CN106356517A CN106356517A CN201610972875.7A CN201610972875A CN106356517A CN 106356517 A CN106356517 A CN 106356517A CN 201610972875 A CN201610972875 A CN 201610972875A CN 106356517 A CN106356517 A CN 106356517A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a plant biomass carbon doped sulfur-nitrogen composite material of cathodes of a sodium ion battery and a lithium ion battery and a preparation method of the plant biomass carbon doped sulfur-nitrogen composite material. The preparation method comprises the following steps: (1) soaking in a pore forming agent; (2) performing high-temperature pre forming and carbonization; (3) washing and drying; (4) performing sulfur and nitrogen source infiltration; and (5) performing high-temperature sulfur-nitrogen doping. The plant biomass carbon doped sulfur-nitrogen composite material has relatively large specific capacity, relatively good charge/discharge multiplying power property and good stability. The preparation method disclosed by the invention is simple and feasible, the prepared electrode material is excellent in chemical stability, plant biomass raw materials are low in price, easy to obtain and wide in source, plant resources or even waste plant resources can be sufficiently utilized, and thus the purpose of environment protection can be achieved.
Description
Technical field
The invention belongs to plant biomass material with carbon element technical field is and in particular to plant biomass carbon doping sulfur nitrogen composite wood
Material and preparation method thereof.
Background technology
Biomass energy is one of important energy source for the survival of mankind, occupies critical role in whole energy resource system.By
Lead to fossil energy resource progressively to face exhaustion in the undue exploitation of the mankind, the new forms of energy of environmental protection and its research of material, open
Send out even more very urgent with integrated application.Biological material has high energy storage, pollution-free, reproducible feature, is superior, tool
The material of standby broad prospect of application.
At present, the material with carbon element being made up of plant biological material has light weight, porosity height, structural stability because of it
The characteristics such as good, easy conductive, have a wide range of applications in battery with the electrochemical energy storing device such as ultracapacitor.Compared to current
The graphite material using on commercial Li-ion battery negative pole, biological material is provided that higher specific capacity, more excellent times
Rate performance and bigger compacted density, are the ideal choses of lithium ion battery negative material of future generation.
However, sending out recently as the quick of the intelligent devices such as New-energy electric vehicle, electronic product, electrical network energy-storage system
Exhibition, the demand exponentially formula of energy storage material particularly lithium resource increases, and the exhausted problem of lithium resource progressively emerges.Sodium ion electricity
Pond, is considered progressively to substitute the novel cell of lithium ion battery, of great interest and research.Due to lithium ion battery
Consistent with sodium-ion battery discharge and recharge ultimate principle, biomass carbon material also has similar application on sodium-ion battery, but
, for sodium-ion battery with lithium ion battery, the former specific capacity is lower, and sodium atom compares lithium atom for same organism matter material with carbon element
Radius is greatly it is simply that hinder one of principal element of sodium atom insert material.The abundant life adapting to sodium-ion battery therefore will be found
Material material with carbon element is it is necessary to modify to its structure.The present invention, carries out the doping of sulfur, nitrogen-atoms, former to biomass material with carbon element
Biomass carbon material interlamellar spacing and defect are increased on son/molecular structure, functionally increases the absorbability of material sodium ion, have
Quick diffusion beneficial to sodium ion and the electric conductivity increasing material with carbon element, thus improve the specific capacity of sodium-ion battery, cycle performance,
The chemical properties such as high rate performance.
Content of the invention
Primary and foremost purpose of the present invention is to provide a kind of sodium-ion battery and lithium ion battery negative plant biomass carbon doping sulfur
Nitrogen composite and preparation method thereof.
Method of the present invention simple possible, the electrode material chemical stability of preparation is excellent, and plant biomass raw material is cheap
It is easy to get, wide material sources, various plant resourceses can be made full use of, including xylophyta series, gramineae plant series, herbaceous plant system
Row, liana series and its industrial wood waste and garbage series, reach environmental protection purpose.
Plant biomass carbon doping sulfur nitrogen composite is layered porous structure, and specific surface area is more than business graphite.With
When, sulfur, N doping increase material interlamellar spacing, are more beneficial for the quick diffusion of ion and increase material conductivity；Doping sulfur nitrogen
Make material on atom and molecular structure in defect occurs, functionally increase the absorbability to sodium ion, lithium ion.This plant
Thing biomass carbon doping sulfur nitrogen composite has higher specific capacity, preferable charge/discharge rate property and good stablizing
Property.
The purpose of the present invention is realized by the following technical solutions.
A kind of sodium-ion battery and the preparation method of lithium ion battery negative plant biomass carbon doping sulfur nitrogen composite,
Comprise the steps:
(1) immerse pore creating material: plant biomass material seal is infiltrated on after 4-24h in nitrate solution, takes out plant
Biological material, is dried；
(2) high temperature pore-creating carbonization: under protective atmosphere, the plant biological material that insulation calcining has been dried；
(3) washing and drying: the carbonate plant biological material that step (2) is obtained is ground to after powder, uses successively
The hydrochloric acid of 0.5-3mol/l and deionized water wash respectively, are dried, and obtain the black powder plant biomass material with carbon element of drying；
(4) sulfur, nitrogen source are penetrated into: sulphur source, nitrogen source and the black powder plant biomass material with carbon element being dried are added to
In ionized water, under the rotating speed of 800～2000r/min, stir 2-6h, be dried, obtain penetrating into sulfur, the plant biomass carbon of nitrogen source
Material；
(5) high temperature dopant sulfur nitrogen: the plant biomass material with carbon element of infiltration sulfur, nitrogen source is incubated calcining under protective atmosphere；
After calcining terminates, cooling, then insulation calcining under air atmosphere, obtain described plant biomass carbon doping sulfur nitrogen composite.
Further, in step (1), described plant biological material includes xylophyta series, herbaceous plant series, rattan
This plant series or plant biomass industrial wood waste and garbage series；Described xylophyta series includes Cotton Gossypii, Flos Rosae Rugosae, jade
Orchid, willow or Citrus；Described herbaceous plant series includes phragmites communiss, Flos Nelumbinises, Oryza sativa L., Herba bromi japonici, Semen Maydiss or bamboo；Described liana system
Row inclusion is led a cow, calabash, Flos Rosae Multiflorae or Caulis Hederae Sinensiies；Described plant biomass industrial wood waste and garbage series include disposable chopsticks
Son, establishment gunnysack, coffee groundss, fallen leaves, rice husk, shell or straw.
Further, in step (1), described nitrate solution is pore creating material, and the concentration of nitrate solution is 0.1-
1mol/l；Described nitrate is one or more of potassium nitrate, sodium nitrate and magnesium nitrate.
Further, in step (2), the temperature of described insulation calcining is 600-900 DEG C, and temperature retention time is 1-6h, heats up
Speed is 5-10 DEG C/min.
Further, in step (4), described sulphur source include one of thiourea, sulphur powder and dodecylbenzene sodium sulfonate with
On；Described nitrogen source includes one or more of carbamide, tripolycyanamide, thiourea, polyaniline and dicyandiamide.
Further, in step (4), the mass ratio of described sulphur source and the black powder plant biomass material with carbon element being dried
For 0.01:1～2:1, described nitrogen source is 0.01:1～2 with the mass ratio of the black powder plant biomass material with carbon element being dried:
1；When the sulphur source adding, nitrogen source are mix sulphur/nitrogen source, as doping sulfur, nitrogen compound or during mixture, sulfur/nitrogen source compound
Or mixture is still 0.01:1～2:1 with the mass ratio of the black powder plant biomass material with carbon element being dried.
Further, step (1), (3), in (4), described drying is dried 6-24h at referring to be placed in 60-100 DEG C in baking oven.
Further, in step (5), the temperature being incubated calcining under described protective atmosphere is 600-900 DEG C, and temperature retention time is
1-6h, heating rate is 5-10 DEG C/min；The rate of temperature fall of described cooling is 5-10 DEG C/min；Under described air atmosphere, insulation is forged
The temperature burnt is 200-350 DEG C, and temperature retention time is 1-3h.
Further, step (2), in (5), described protective atmosphere is inert atmosphere, reducing atmosphere or mixed atmosphere；Described
Inert atmosphere refers to nitrogen or argon, and described reducing atmosphere refers to hydrogen；Described mixed atmosphere refers to nitrogen-hydrogen mixed gas or argon
Gas-hydrogen gas mixture, wherein hydrogen volume ratio are 0%-10%.
The sodium-ion battery being obtained by the described preparation method of any of the above item and lithium ion battery negative plant biomass carbon
Doping sulfur nitrogen composite.
The second object of the present invention is to provide a kind of sodium-ion battery negative pole and the plant carbon of used as negative electrode of Li-ion battery to mix
The purposes of miscellaneous sulfur nitrogen material, described negative pole plant carbon doping sulfur nitrogen composite is used for preparing sodium ion secondary battery and lithium ion
Secondary cell.
Compared with prior art, the invention has the advantages that and technique effect:
(1) the plant carbon doping sulfur nitrogen composite prepared by is amorphous carbon material.
(2) the plant biomass carbon doping sulfur nitrogen composite prepared by increases with sulphur source, nitrogen source content, and material is bar-shaped
Fiber is fewer, and sheet-like fiber is more.
(3) sodium-ion battery of the plant biomass carbon doping sulfur nitrogen composite preparation being obtained using the present invention is had relatively
Height coulombic efficiency first, all more than 90%, and the sodium-ion battery being obtained has capacity height, stability preferably, has preferably
Charge-discharge magnification performance.
(4) lithium ion battery of the plant biomass carbon doping sulfur nitrogen composite preparation being obtained using the present invention is had relatively
High first charge-discharge capacity, higher capacity and cycle performance, and compare prepared sodium-ion battery there is more excellent discharge and recharge
High rate performance.
Brief description
Fig. 1 is the xrd of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
Collection of illustrative plates；
Fig. 2 a is that the cotton fruit fibrous carbon that embodiment 1 thiourea is obtained for 0.1:1 with cotton fruit fibrous carbon mass ratio is mixed
The sem figure of miscellaneous sulfur nitrogen material；
Fig. 2 b is the cotton fruit fiber carbon doping that embodiment 1 thiourea is obtained for 1:1 with cotton fruit fibrous carbon mass ratio
The sem figure of sulfur nitrogen material；
Fig. 2 c is the sem figure of embodiment 1 cotton fruit fiber material with carbon element；
Fig. 3 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For anode material of lithium-ion battery first charge-discharge curve；
Fig. 4 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For circulating 600 Capacity Plans under anode material of lithium-ion battery 2.0a/g electric current density；
Fig. 5 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For anode material of lithium-ion battery high rate performance figure；
Fig. 6 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For lithium ion battery negative material first charge-discharge curve；
Fig. 7 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For circulating 150 Capacity Plans under lithium ion battery negative material 1.0a/g electric current density；
Fig. 8 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For circulating 200 Capacity Plans under lithium ion battery negative material 2.0a/g electric current density；
Fig. 9 is the work of the prepared cotton fruit fiber material with carbon element of embodiment 1 and cotton fruit fiber carbon doping sulfur nitrogen material
For lithium ion battery negative material high rate performance figure.
Specific embodiment
Following examples may be better understood the present invention, but the present invention is not limited to following examples.
Embodiment 1
Prepare cotton fruit fiber carbon doping sulfur nitrogen composite:
(1) 15mmol magnesium nitrate is dissolved in 20ml deionized water, by 1.5g cotton fruit fibrous material immersion preparation
In magnesium nitrate solution, after sealing infiltration 24h, it is placed in 70 DEG C of baking ovens 24h to being completely dried.
(2) material of insulation calcining drying in a nitrogen atmosphere, heating rate is 8 DEG C/min, and holding temperature is 800
DEG C, temperature retention time is 3h, obtains the material after high temperature pore-creating carbonization；
(3) hydrochloric acid and the deionized water of 3mol/l after the material after high temperature pore-creating carbonization is ground to powder, are used successively
Wash three times respectively, be placed in 60 DEG C of drying in oven 24h to being completely dried, obtain the black powder cotton fruit fiber of drying
Material with carbon element；
(4) thiourea is added to according to following mass ratio respectively with the black powder cotton fruit fiber material with carbon element being dried
In deionized water: (a) thiourea is 0 with the mass ratio of cotton fruit fiber material with carbon element；(b) thiourea and cotton fruit fiber material with carbon element
Mass ratio be 0.1:1；C () thiourea is 1:1 with the mass ratio of cotton fruit fiber material with carbon element；Under the rotating speed of 1500r/min
Stirring 5h, is placed in 20h in 80 DEG C of baking ovens and, to being completely dried, obtains penetrating into sulfur, the cotton fruit fiber material with carbon element of nitrogen source；
(5) cotton fruit fiber material with carbon element 800 DEG C of insulation calcinings under nitrogen atmosphere of sulfur, nitrogen source, temperature retention time are penetrated into
For 3h, heating rate is 8 DEG C/min；Cooling, rate of temperature fall is 8 DEG C/min, 300 DEG C of insulation calcinings, insulation under air atmosphere
Time is 1h, obtains cotton fruit fiber carbon doping sulfur nitrogen composite, referred to as csn-0, csn-0.1, csn-1.
1st, structural analyses
Prepared cotton fruit fiber carbon doping sulfur nitrogen composite csn-0, the xrd of csn-0.1, csn-1 schemes as Fig. 1 institute
Show, as shown in Figure 1, prepared cotton fruit fiber carbon doping sulfur nitrogen composite is amorphous carbon material.
Fig. 2 a is the embodiment 1 thiourea cotton fruit fiber more prepared than for 0.1:1 with cotton fruit fibrous carbon quality of materials
The sem figure of carbon doping sulfur nitrogen material；Fig. 2 b is that embodiment 1 thiourea is obtained for 1:1 with cotton fruit fiber carbon carbon material mass ratio
Cotton fruit fiber carbon doping sulfur nitrogen material sem figure；Fig. 2 c is the sem figure of embodiment 1 cotton fruit fiber material with carbon element；By
Fig. 2 a, Fig. 2 b, Fig. 2 c understand, prepared cotton fruit fiber carbon doping sulfur nitrogen composite increases with sulphur source, nitrogen source content
Plus, material rod-like fibre is fewer, and sheet-like fiber is more.
2nd, chemical property analysis
Born using the cotton fruit fiber carbon doping sulfur nitrogen composite being obtained and cotton fruit fiber material with carbon element as battery
Pole material, assembling cr2032 type sodium ion button cell and cr2032 type lithium-ion button battery in glove box.Implemented
In battery thermostat temperature at 25 DEG C, carry out filling circulation discharge test and high rate performance test in 0.01v-3v voltage range.
(1) sodium-ion battery
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as sodium-ion battery
Negative material first charge-discharge curve as shown in figure 3, as Fig. 3, the sodium implemented with cotton fruit fiber carbon doping sulfur nitrogen material
Ion battery has the feature that coulombic efficiency first is higher, all more than 90%.
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as sodium-ion battery
Negative material circulates 600 Capacity Plans as shown in figure 4, as shown in Figure 4 under 2.0a/g electric current density, with cotton fruit fibrous carbon
It is high that the doping sodium-ion battery implemented of sulfur nitrogen material has a capacity, the preferable feature of stability, initial charge specific capacitance and
600 capacity of circulation are as shown in table 1.
Table 1 initial charge specific capacitance and 600 capacity of circulation
| Capacity (mah/g) | csn-0 | csn-0.1 | csn-1 |
| First | 266.6 | 549.8 | 468.2 |
| 600 times | 249.4 | 476.1 | 371.2 |
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as sodium-ion battery
Negative material high rate performance figure as shown in figure 5, as shown in Figure 5, the sodium implemented with cotton fruit fiber carbon doping sulfur nitrogen material
Ion battery has preferable charge-discharge magnification performance.
(2) lithium ion battery
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as lithium ion battery
Negative material first charge-discharge curve is as shown in fig. 6, it will be appreciated from fig. 6 that implemented with cotton fruit fiber carbon doping sulfur nitrogen material
Lithium ion battery there is higher first charge-discharge capacity.
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as lithium ion battery
Negative material circulates 150 Capacity Plans as shown in Figure 7, circulate 200 times under 2.0a/g electric current density under 1.0a/g electric current density
Capacity Plan is as shown in figure 8, from Fig. 7, Fig. 8, the lithium ion battery implemented with cotton fruit fiber carbon doping sulfur nitrogen material
There is higher capacity and cycle performance, initial charge specific capacity, circulation 150 times, 200 capacity and coulombic efficiency such as table 2 institute
Show.
Table 2 initial charge specific capacity, circulation volume and coulombic efficiency
Prepared cotton fruit fiber material with carbon element and cotton fruit fiber carbon doping sulfur nitrogen material are as lithium ion battery
As shown in figure 9, as shown in Figure 9, carbon doping sulfur nitrogen material is as the prepared lithium ion of negative material for negative material high rate performance figure
The material with carbon element that the high rate performance of battery is higher than the sulfur nitrogen that undopes is obtained lithium ion battery high rate performance.
Embodiment 2
Prepare roseleaf carbon doping sulfur nitrogen composite:
(1) 10mmol magnesium nitrate is dissolved in 20ml deionized water, the roseleaf material of 1.5g dehydrate is immersed
In the magnesium nitrate solution prepared, after sealing infiltration 24h, it is placed in 80 DEG C of baking ovens 20h to being completely dried；
(2) material of insulation calcining drying in a nitrogen atmosphere, heating rate is 10 DEG C/min, and holding temperature is 600
DEG C, temperature retention time is 6h, obtains the material of high temperature pore-creating carbonization；
(3) after the material that high temperature pore-creating carbonization obtain is ground to powder, with hydrochloric acid and the deionization moisture of 3mol/l
Not Xi Di three times, be placed in 60 DEG C of drying in oven 24h to being completely dried, obtain drying black powder roseleaf carbon materials
Material；
(4) by sulphur powder, carbamide be dried black powder roseleaf material with carbon element according to 0.05:0.05:1 mass ratio
It is added in deionized water, stir 3h under the rotating speed of 800r/min, be placed in 24h in 60 DEG C of baking ovens and, to being completely dried, oozed
Enter the roseleaf material with carbon element of sulfur, nitrogen source；
(5) roseleaf material with carbon element 600 DEG C of insulation calcinings under argon atmosphere of sulfur, nitrogen source are penetrated into, temperature retention time is 6h,
Heating rate is 10 DEG C/min；Cooling, rate of temperature fall is 10 DEG C/min, 350 DEG C of calcinings under air atmosphere, and temperature retention time is
1.5h, obtains roseleaf carbon doping sulfur nitrogen composite.
Prepared roseleaf carbon doping sulfur nitrogen composite is amorphous carbon material, for sodium-ion battery and lithium ion
Battery is respectively provided with higher charge/discharge capacity.
Embodiment 3
Prepare oat grain carbon doping sulfur nitrogen composite:
(1) 20mmol sodium nitrate is dissolved in 20ml deionized water, the oat grain material immersion of 1.5g dehydrate is joined
In the sodium nitrate solution of system, after sealing infiltration 24h, it is placed in 80 DEG C of baking ovens 18h to being completely dried；
(2) material of insulation calcining drying under an argon atmosphere, heating rate is 5 DEG C/min, and holding temperature is 750
DEG C, temperature retention time is 3h, obtains the material of high temperature pore-creating carbonization；
(3) material that high temperature pore-creating carbonization obtain is ground to hydrochloric acid and the deionization moisture after powder with 2.8mol/l
Not Xi Di three times, be placed in 80 DEG C of drying in oven 18h to being completely dried, obtain drying black powder oat grain material with carbon element；
(4) sulphur powder, dicyandiamide and the black powder oat grain material with carbon element being dried are added according to the mass ratio of 0.1:0.1:1
Enter in deionized water, stir 4h under the rotating speed of 1400r/min, be placed in 20h in 80 DEG C of baking ovens and, to being completely dried, penetrated into
Sulfur, the oat grain material with carbon element of nitrogen source；
(5) oat grain material with carbon element 900 DEG C of insulation calcinings under argon and 5% atmosphere of hydrogen of sulfur, nitrogen source are penetrated into, during insulation
Between be 3h, heating rate be 5 DEG C/min；Cooling, rate of temperature fall is 5 DEG C/min, and 350 DEG C of calcinings under air atmosphere, during insulation
Between be 1h, obtain oat grain carbon doping sulfur nitrogen composite.
Prepared oat grain carbon doping sulfur nitrogen composite is amorphous carbon material, for sodium-ion battery and lithium-ion electric
Pond is respectively provided with higher charge/discharge capacity.
Embodiment 4
Preparation waste straw carbon doping sulfur nitrogen composite:
(1) 20mmol potassium nitrate is dissolved in 20ml deionized water, by 2g through dehydrate and physical pulverization discarded straw
The immersion of stalk material is in the potassium nitrate solution of preparation, after sealing infiltration 12h, is placed in 60 DEG C of baking ovens 24h to being completely dried；
(2) material of insulation calcining drying in a nitrogen atmosphere, heating rate is 8 DEG C/min, and holding temperature is 900
DEG C, temperature retention time is 1h, obtains the material of high temperature pore-creating carbonization；
(3) material that high temperature pore-creating carbonization obtain is ground to after powder with the hydrochloric acid of 3mol/l and deionized water respectively
Washing three times, is placed in 100 DEG C of drying in oven 6h to being completely dried, and obtains the black powder waste straw material with carbon element of drying；
(4) by thiourea and plant biomass material with carbon element respectively according to the mass ratio of 0.01:1,1:1 and 2:1 be added to from
In sub- water, under the rotating speed of 2000r/min, stir 4h, be placed in 15h in 80 DEG C of baking ovens and, to being completely dried, obtain penetrating into sulfur, nitrogen source
Waste straw material with carbon element；
(5) penetrate into waste straw material with carbon element 900 DEG C of insulation calcinings under argon and 10% atmosphere of hydrogen of sulfur, nitrogen source, protect
The warm time is 1h, and heating rate is 7.5 DEG C/min；Cooling, rate of temperature fall is 7.5 DEG C/min, forges for 300 DEG C under air atmosphere
Burn, be incubated 3h respectively, obtain waste straw carbon doping sulfur nitrogen composite.
Prepared waste straw carbon doping sulfur nitrogen composite is amorphous carbon material, for sodium-ion battery and lithium ion
Battery is respectively provided with higher charge/discharge capacity.
Embodiment 5
Preparation is led a cow vinc fiber carbon doping sulfur nitrogen composite:
(1) 15mmol magnesium nitrate is dissolved in 20ml deionized water, by 2g through dehydrate and physical pulverization rattan of leading a cow
Material immersion is in the magnesium nitrate solution of preparation, after sealing infiltration 4h, is placed in 100 DEG C of baking ovens 6h to being completely dried；
(2) under the mixed atmosphere of nitrogen and 5% hydrogen, the material of drying is calcined in insulation, and heating rate is 8 DEG C/min,
Holding temperature is 800 DEG C, and temperature retention time is 3h, obtains the material of high temperature pore-creating carbonization
(3) material that high temperature pore-creating carbonization obtain is ground to hydrochloric acid and the deionization moisture after powder with 0.5mol/l
Not Xi Di three times, be placed in 60 DEG C of drying in oven 24h to being completely dried, the black powder obtaining drying is led a cow vinc fiber carbon materials
Material；
(4) by dodecylbenzene sodium sulfonate, tripolycyanamide be dried black powder lead a cow vinc fiber material with carbon element according to
The mass ratio of 1:1:1 is added in deionized water, stirs 4h under the rotating speed of 1200r/min, is placed in 6h in 100 DEG C of baking ovens extremely complete
White drying, obtains penetrating into sulfur, the vinc fiber material with carbon element of leading a cow of nitrogen；
(5) lead a cow vinc fiber material with carbon element 800 DEG C of insulation calcinings, insulation under nitrogen and 5% atmosphere of hydrogen of sulfur, nitrogen are penetrated into
Time is 3h, and heating rate is 5 DEG C/min；Cooling, rate of temperature fall is 10 DEG C/min, 200 DEG C of calcinings under air atmosphere, insulation
Time is 3h, obtains vinc fiber carbon doping sulfur nitrogen composite of leading a cow.
Prepared vinc fiber carbon doping sulfur nitrogen composite of leading a cow is amorphous carbon material, for sodium-ion battery and lithium from
Sub- battery is respectively provided with higher charge/discharge capacity.
Claims (10)
1. the preparation method of a kind of sodium-ion battery and lithium ion battery negative plant biomass carbon doping sulfur nitrogen composite, its
It is characterised by, comprise the steps:
(1) immerse pore creating material: plant biomass material seal is infiltrated on after 4-24h in nitrate solution, takes out plant biological
Material, is dried；
(2) high temperature pore-creating carbonization: under protective atmosphere, the plant biological material that insulation calcining has been dried；
(3) washing and drying: the carbonate plant biological material that step (2) is obtained is ground to after powder, uses 0.5- successively
The hydrochloric acid of 3mol/l and deionized water wash respectively, are dried, and obtain the black powder plant biomass material with carbon element of drying；
(4) sulfur, nitrogen source are penetrated into: sulphur source, nitrogen source and the black powder plant biomass material with carbon element being dried are added to deionization
In water, under the rotating speed of 800 ~ 2000r/min, stir 2-6h, be dried, obtain penetrating into sulfur, the plant biomass material with carbon element of nitrogen source；
(5) high temperature dopant sulfur nitrogen: the plant biomass material with carbon element of infiltration sulfur, nitrogen source is incubated calcining under protective atmosphere；Calcining
After end, cooling, then insulation calcining under air atmosphere, obtain described plant biomass carbon doping sulfur nitrogen composite.
2. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (1), described plant biological material includes xylophyta series, draft
Plant series, liana series or plant biomass industrial wood waste and garbage series；Described xylophyta series includes
Cotton Gossypii, Flos Rosae Rugosae, Magnolia denudata, willow or Citrus；Described herbaceous plant series includes phragmites communiss, Flos Nelumbinises, Oryza sativa L., Herba bromi japonici, Semen Maydiss or bamboo；Institute
State liana series include leading a cow, calabash, Flos Rosae Multiflorae or Caulis Hederae Sinensiies；Described plant biomass industrial wood waste and garbage series
Including throwaway chopsticks, establishment gunnysack, coffee groundss, fallen leaves, rice husk, shell or straw.
3. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (1), described nitrate solution is pore creating material, and nitrate solution
Concentration is 0.1-1mol/l；Described nitrate is one or more of potassium nitrate, sodium nitrate and magnesium nitrate.
4. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (2), the temperature of described insulation calcining is 600-900 DEG C, temperature retention time
For 1-6h, heating rate is 5-10 DEG C/min.
5. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (4), described sulphur source includes thiourea, sulphur powder and dodecylbenzene sodium sulfonate
One or more of；Described nitrogen source includes one or more of carbamide, tripolycyanamide, thiourea, polyaniline and dicyandiamide.
6. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (4), described sulphur source and the black powder plant biomass carbon being dried
The mass ratio of material is 0.01:1 ~ 2:1, and described nitrogen source with the mass ratio of the black powder plant biomass material with carbon element being dried is
0.01:1~2:1；When the sulphur source adding, nitrogen source are mix sulphur/nitrogen source, as doping sulfur, nitrogen compound or during mixture, sulfur/nitrogen
Source compound or mixture are still 0.01:1 ~ 2:1 with the mass ratio of the black powder plant biomass material with carbon element being dried.
7. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: step (1), (3), in (4), described drying refers to be placed in 60-100 DEG C in baking oven
Under 6-24h is dried.
8. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (5), the temperature being incubated calcining under described protective atmosphere is 600-900
DEG C, temperature retention time is 1-6h, and heating rate is 5-10 DEG C/min；The rate of temperature fall of described cooling is 5-10 DEG C/min；Described sky
The temperature that atmosphere encloses lower insulation calcining is 200-350 DEG C, and temperature retention time is 1-3h.
9. a kind of sodium-ion battery according to claim 1 is multiple with lithium ion battery negative plant biomass carbon doping sulfur nitrogen
The preparation method of condensation material it is characterised in that: in step (2), (5), described protective atmosphere is inert atmosphere, reducing atmosphere or mixed
Close atmosphere；Described inert atmosphere refers to nitrogen or argon, and described reducing atmosphere refers to hydrogen；Described mixed atmosphere refers to nitrogen-hydrogen to be mixed
Close gas or argon-hydrogen mixed gas, wherein hydrogen volume ratio is 0%-10%.
10. the sodium-ion battery that preparation method described in any one of claim 1-9 is obtained and lithium ion battery negative plant give birth to
Material carbon doping sulfur nitrogen composite.
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