CN109301246A - A kind of sulfur doping hard carbon material, preparation method and its kalium ion battery as cathode - Google Patents
A kind of sulfur doping hard carbon material, preparation method and its kalium ion battery as cathode Download PDFInfo
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- CN109301246A CN109301246A CN201811142962.5A CN201811142962A CN109301246A CN 109301246 A CN109301246 A CN 109301246A CN 201811142962 A CN201811142962 A CN 201811142962A CN 109301246 A CN109301246 A CN 109301246A
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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
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The present invention relates to a kind of sulfur doping hard carbon material, preparation method and its as the kalium ion battery of cathode, the hard carbon material has porous structure, and the sulphur atom is at least partly distributed in the inside of the hard carbon material.The preparation method of the hard carbon material includes: (1) by sulphur coal pickling, is then impregnated in alkaline solution, and basic products are made；(2) under protective atmosphere, basic products are heat-treated, hard carbon material is made；(3) hard carbon material is subjected to acid solution immersion, washing, filtering and drying course.For the present invention using sulphur coal as raw material, hard carbon material pore size obtained can satisfy the requirement of potassium ion intercalation/deintercalation, and at the same time, the auto-dope of element sulphur original position assigns the new electro-chemical activity of material and more preferably cellular structure in the surface and carbon base body of material.In carbon material produced by the present invention element sulphur be more evenly distributed, production cost it is less expensive.
Description
Technical field
The invention belongs to hard carbon material technical fields, and in particular to a kind of sulfur doping hard carbon material, preparation method and its
As the kalium ion battery of cathode, the sulfur doping hard carbon material is used for kalium ion battery field.
Background technique
Currently, secondary cell of new generation has caused the broad interest of scientific researcher, lithium ion battery has energy close
Outstanding advantages of spending height, having extended cycle life and is pollution-free, it has also become the mainstream of Battery Market, and start to be applied to drive electronic vapour
Vehicle.But with the large-scale application of lithium ion battery, the price of lithium and the finiteness of resource are increasingly worried by people.In recent years
Come, many novel substitution energy-storage batteries come into being and rapidly develop, and mainly include sodium ion, potassium ion, magnesium ion, calcium ion
Equal secondary cells.
Kalium ion battery has many advantages as novel substitution energy-storage battery, rich content of the potassium resource in the earth's crust,
It is cheap；The normal reduction potential of kalium ion battery and lithium ion battery is closest, thus energy density is high；Potassium ion electricity
Pond electrolyte electrochemical activity is high, is conducive to the transmission of ion and electronics.Kalium ion battery negative electrode material reported at present
Study less, the emphasis of research is still concentrated on the carbon material, however, since potassium ion radius is excessive and the higher chemistry of potassium
Activity, the Carbon anode performance commonly used in lithium, sodium-ion battery is bad,.
CN105810914A discloses a kind of sodium-ion battery sulfur doping porous carbon materials and preparation method thereof, and sulfur doping is more
Hole carbon material is made up of in carbon material sulphur chemical doping, and the carbon material has loose porous spongelike structure.Institute
Stating preparation method is that metal inorganic salt and organic ligand are prepared metal-organic framework material by situ synthesis, and metal is organic
After frame material and sulphur powder pass through ground and mixed, it is placed under inert gas, first carries out Low Temperature Heat Treatment, then carry out high temperature cabonization,
Carbonized product is washed, it is dry to get.Sulfur doping porous carbon materials made from the method have as sodium-ion battery cathode
Excellent long circulating stability energy, good high rate performance and height ratio capacity etc., but its preparation process are complicated, poor controllability,
It is difficult to industrialized production.
CN107317015A discloses a kind of method that zinc oxide/carbon composite prepares kalium ion battery for cathode, adopts
The method for taking high temperature solid-phase sintering to close prepares kalium ion battery negative electrode material, in preparation process, regulates and controls technology ginseng in reaction process
Number obtains zinc oxide/carbon composite, and using zinc oxide/carbon composite as the negative electrode material of kalium ion battery, potassium is made
Ion battery.The synthetic method is simple, and operating procedure is controllable, is easily enlarged production, but the material property prepared is unable to satisfy
Kalium ion battery performance requirement.
CN108039464A discloses a kind of self-supporting sodium ions to potassium ions battery material and the preparation method and application thereof, described
Self-supporting sodium ions to potassium ions battery material is specially porous sulfur doping graphene aerogel, and the content of sulphur is 2~10wt%, knot
Structure is the three-dimensional structure that flake graphite alkene is self-assembly of.Graphene oxide water solution, which first reacts with ammonia water, to be freeze-dried to obtain afterwards
Graphene aerogel, then react to obtain porous sulfur doping graphene aerogel at high temperature with sulphur steam.By the porous sulfur doping
Sodium ions to potassium ions battery cathode can be used in a manner of self-supporting after graphene aerogel compacting.The porous sulfur doping graphene gas
Gel has excellent cycle performance and high rate performance as the sodium ions to potassium ions battery of cathode, but preparation method is complicated, Wu Fagong
Industry metaplasia produces.
So this field needs to develop a kind of carbon negative pole material for kalium ion battery, make it have stable structure,
Suitable electrochemistry deintercalation potassium platform, specific capacity is big, is suitable for industrialized production.
Summary of the invention
In view of the deficiencies of the prior art, one of the objects of the present invention is to provide a kind of sulfur doping hard carbon materials, described hard
Carbon material has porous structure, and the sulphur atom is at least partly distributed in the inside of the hard carbon material.
The porous carbon materials that the present invention designs can match requirement of the kalium ion battery to negative electrode material, the doping of sulphur atom
The interlamellar spacing of carbon material can be increased and obtain more preferably cellular structure, meet the requirement of potassium ion intercalation/deintercalation.
In sulfur doping carbon material provided by the invention, sulphur atom can substitute the carbon potential in carbon base body, due to the electricity of sulphur atom
Negativity is close with carbon atom, but the radius of sulphur atom is but greater than carbon atom, thus the sulphur atom mixed in hard carbon material can be beaten
The broken original balanced structure of hard carbon material assigns the new electro-chemical activity of material and more preferably cellular structure, is more advantageous to potassium
The migration and diffusion process of ion.On the one hand the specific capacity of material can be improved in the presence of sulphur atom, on the other hand can assign
The new electro-chemical activity of hard carbon material.
Sulphur atom of the present invention is at least partly distributed in the inside of the hard carbon material, is distributed in hard carbon material for sulphur atom
The surface of material and internal or sulphur atom are all distributed in the inside of material.
Preferably, in hard carbon material of the present invention sulfur content be 2~10wt%, such as 2.5wt%, 3wt%, 4wt%,
5wt%, 6wt%, 7wt%, 8wt%, 9wt% etc..
Preferably, the hard carbon material has hierarchical porous structure.
It is further preferred that micropore, mesoporous and macropore is distributed in the hard carbon material.
Be known as micropore of the aperture less than 2nm, aperture are known as greatly in the referred to as mesoporous of the hole 2~50nm, aperture greater than 50nm's
Hole.
Preferably, pore-size distribution 0.5nm~2 μm of the hard carbon material, for example, 1nm, 2nm, 10nm, 20nm, 500nm,
200nm, 500nm, 1 μm etc..
The aperture of hard carbon material is too small, and it is difficult to will lead to potassium ion intercalation/deintercalation in charge and discharge process；The hole of hard carbon material
Diameter is excessive, and material activity position is less and structure is easy to collapse.
Preferably, 280~1189m of specific surface area of the hard carbon material2/ g, such as 300m2/g、400m2/g、500m2/
g、600m2/g、700m2/g、800m2/g、1000m2/ g etc..
The surface area of hard carbon material is too small, can be difficult to provide more storage active sites.
The second object of the present invention is to provide a kind of preparation method of sulfur doping hard carbon material, the preparation method includes such as
Lower step:
(1) it by sulphur coal pickling, is then impregnated in alkaline solution, basic products is made；
(2) under protective atmosphere, basic products are heat-treated, hard carbon material is made.
The present invention uses sulphur coal (sulfur content >=3wt%) for raw material, and sulfur doping hard carbon material is prepared in auto-dope in situ
The classification cavernous structure suitable for kalium ion battery, while sulphur coal is made using the classification pipe cell structure of sulphur coal itself in material
In element sulphur the specific capacity and electro-chemical activity of material can be improved.
Auto-dope in situ can make sulphur atom be not only present in material surface, more have comparable a part to be present in carbon base body
In, and then break the original balanced structure of hard carbon material, assign the new electro-chemical activity of material and more preferably cellular structure.
Preferably, the sulfur content of sulphur coal of the present invention is 3~8wt%, such as 4wt%, 5wt%, 6wt%, 7wt%
Deng.
Preferably, the process of step (1) described pickling includes: to crush the sulphur coal, is impregnated in acid solution, mistake
Filter, it is dry.
Preferably, the acid solution includes hydrochloric acid solution and/or hydrofluoric acid solution.
Preferably, the concentration of the hydrochloric acid solution be 0.5~5mol/L, such as 1mol/L, 1.5mol/L, 1.8mol/L,
2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L etc..
Preferably, the concentration of the hydroflouric acid solution be 0.1~1mol/L, such as 0.2mol/L, 0.3mol/L,
0.4mol/L, 0.5mol/L, 0.6mol/L, 0.7mol/L, 0.8mol/L, 0.9mol/L etc..
Preferably, the time of the pickling be 12~28h, such as 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h,
21h, 22h, 23h, for 24 hours, 25h, 26h, 27h etc..
Pickling can remove the ash content (mineral) in sulphur coal, it is avoided to influence the chemical property of hard carbon material.
Preferably, solute and the sulphur coal mass ratio after pickling are 0.5:1~4:1, example in step (1) described alkaline solution
Such as 1:1,1.5:1,2:1,2.5:1,3:1,3.5:1.
Solute is less than 0.5:1 with the sulphur coal mass ratio after pickling in alkaline solution, and activator levels are very few, it is difficult to generate
Big specific surface area；Solute is greater than 4:1 with the sulphur coal mass ratio after pickling in alkaline solution, can generate a large amount of micropores, in turn
Pore structure is caused to be destroyed, mechanical strength reduces.
Preferably, the alkaline solution includes KOH solution and/or NaOH solution.
Preferably, the time being impregnated in alkaline solution be 12~28h, such as 13h, 14h, 15h, 16h, 17h,
18h, 19h, 20h, 21h, 22h, 23h, for 24 hours, 25h, 26h, 27h etc..
Preferably, the drying process is freeze-drying.
Preferably, step (2) the of the present invention heat treatment temperature be 600~900 DEG C, such as 650 DEG C, 700 DEG C, 750 DEG C,
800 DEG C, 850 DEG C etc..
Heat treatment temperature be higher than 900 DEG C, may cause carbon material degree of graphitization raising, reduce interlamellar spacing, influence potassium from
Son insertion abjection；Heat treatment temperature is lower than 600 DEG C, and it is incomplete to carbon conversion and activator pore-creating to may cause coal, thus shadow
Ring storage potassium performance.
Preferably, the heating rate of the heat treatment be 0.5~5 DEG C/min, such as 1 DEG C/min, 1.5 DEG C/min, 2 DEG C/
Min, 2.5 DEG C/min, 3 DEG C/min, 3.5 DEG C/min, 4 DEG C/min, 4.5 DEG C/min etc..
Preferably, the time of the heat treatment is 1~6h, such as 2h, 3h, 4h, 5h etc..
Preferably, the protective atmosphere includes inert atmosphere, preferably includes nitrogen atmosphere, argon atmosphere and helium atmosphere
In any one or at least two combination, such as argon atmosphere, nitrogen atmosphere etc..
Preferably, step (3) are carried out after step (2) of the present invention: hard carbon material is subjected to acid solution immersion, washing, mistake
Filter and drying course.
Preferably, the acid solution includes hydrochloric acid solution and/or hydrofluoric acid solution.
Further preferably, the acid solution is hydrochloric acid solution.
Preferably, the concentration of the acid solution be 0.5~5mol/L, such as 1mol/L, 1.5mol/L, 1.8mol/L,
2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L etc..
Preferably, the time of the pickling be 6~for 24 hours, such as 7h, 8h, 9h, 10h, 11h, 12h, 13h, 15h, 17h,
19h, 21h, 23h etc..
Preferably, the washing includes that deionized water is washed.
Preferably, the temperature of the drying is 80~120 DEG C, such as 85 DEG C, 90 DEG C, 95 DEG C, 100 DEG C, 105 DEG C, 110 DEG C
Deng.
As optimal technical scheme, the preparation method of sulfur doping hard carbon material of the present invention includes the following steps:
(1) sulphur coal that sulfur content is 3~8% after 12~28h of pickling, is impregnated in 12 in alkaline solution in acid solution
~28h, wherein aqueous slkali solute and the sulphur coal mass ratio after pickling are 0.5:1~4:1, and basic products are made after freeze-drying；
(2) by basic products with the heating rate of 0.5~5 DEG C/min to being heat-treated at a temperature of 600~900 DEG C, heat preservation 1
Hard carbon material is made in~6h；
(3) hard carbon material impregnates to 6 in the hydrochloric acid solution of 0.5~5mol/L~for 24 hours, deionized water washing, filtering and
80~120 DEG C of drying.
The three of the object of the invention are to provide a kind of purposes of sulfur doping hard carbon material as described in the first purpose, the hard carbon
Material is used for field of batteries, is preferred for kalium ion battery field.
Preferably, the hard carbon material is used as the negative electrode material of kalium ion battery.
The four of the object of the invention are to provide a kind of kalium ion battery, and the kalium ion battery includes described in the first purpose
Sulfur doping hard carbon material.
Preferably, the negative electrode material of the kalium ion battery includes sulfur doping hard carbon material described in the first purpose.
Preferably, one of for the purpose of the negative electrode material of the kalium ion battery described in sulfur doping hard carbon material.
Compared with prior art, the invention has the following beneficial effects:
(1) in the sulfur doping hard carbon material that the present invention designs, the doping of sulphur atom can increase the interlamellar spacing of carbon material simultaneously
More preferably cellular structure is obtained, meets the requirement of potassium ion intercalation/deintercalation, the negative electrode material as kalium ion battery shows excellent
Different chemical property.
(2) using sulphur coal as raw material, element sulphur is present in material matrix the present invention, introduces sulphur source without external, relatively
In introducing carbon material made from sulphur source in outside, in carbon material produced by the present invention element sulphur be more evenly distributed, production cost more
It is cheap.
(3) present invention prepares sulfur doping hard carbon material using auto-dope in situ, can not only sulphur atom be made to be present in material
Surface more has comparable a part to be present in carbon base body, and then breaks the original balanced structure of hard carbon material, and it is new to assign material
Electro-chemical activity and more preferably cellular structure.
Detailed description of the invention
Fig. 1 is the resulting sulfur doping hard carbon material SEM of embodiment 1 figure；
Fig. 2 is the resulting sulfur doping hard carbon material XRD spectrum of embodiment 1；
Fig. 3 is the resulting sulfur doping hard carbon material SEM of embodiment 11 figure；
Fig. 4 is the resulting sulfur doping hard carbon material XRD spectrum of embodiment 11.
Specific embodiment
Of the invention for ease of understanding, it is as follows that the present invention enumerates embodiment.Those skilled in the art are it will be clearly understood that the implementation
Example is only to aid in the understanding present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
(1) sulphur coal that sulfur content is 4.27% after pickling for 24 hours, is impregnated in NaOH solution in 1mol/L hydrochloric acid solution
In for 24 hours, wherein the sulphur coal mass ratio after NaOH solution solute and pickling is 1:1, and basic products are made after freeze-drying；
(2) by basic products with the heating rate of 2 DEG C/min to being heat-treated at a temperature of 800 DEG C, keep the temperature 2h, hard carbon be made
Material；
(3) hard carbon material is impregnated to 12h, deionized water washing, filtering and 100 DEG C of bakings in the hydrochloric acid solution of 2mol/L
Dry, obtaining sulfur content is 3.75%, and pore-size distribution is the sulfur doping hard carbon material of 0.5nm~2 μm, and Fig. 1 is the hard carbon material
SEM figure, carbon is in honeycomb structure as can be seen from Figure, and Fig. 2 is the XRD spectrum of the hard carbon material, described hard as seen from the figure
Carbon material is amorphous hard carbon.
Embodiment 2
The difference from embodiment 1 is that the sulfur content of step (1) medium-high sulfur coal is 3%, obtaining sulfur content is 2.79%
Sulfur doping hard carbon material.
Embodiment 3
The difference from embodiment 1 is that the sulfur content of step (1) medium-high sulfur coal is 8%, obtaining sulfur content is 7.49%
Sulfur doping hard carbon material.
Embodiment 4
The difference from embodiment 1 is that the sulfur content of step (1) medium-high sulfur coal is 2.5%, obtaining sulfur content is 2%
Sulfur doping hard carbon material.
Embodiment 5
The difference from embodiment 1 is that aqueous slkali solute and the sulphur coal mass ratio after pickling are 0.5:1 in step (1),
Obtain the sulfur doping hard carbon material that sulfur content is 4.02%.
Embodiment 6
The difference from embodiment 1 is that aqueous slkali solute and the sulphur coal mass ratio after pickling are 4:1 in step (1), obtain
The sulfur doping hard carbon material for being 3.58% to sulfur content.
Embodiment 7
The difference from embodiment 1 is that aqueous slkali solute and the sulphur coal mass ratio after pickling are 0.3:1 in step (1),
Obtain the sulfur doping hard carbon material that sulfur content is 4.03%.
Embodiment 8
The difference from embodiment 1 is that aqueous slkali solute and the sulphur coal mass ratio after pickling are 5:1 in step (1), obtain
The sulfur doping hard carbon material for being 3.31% to sulfur content.
Embodiment 9
The difference from embodiment 1 is that heat treatment temperature is 600 DEG C in step (2), the sulphur that sulfur content is 3.82% is obtained
Adulterate hard carbon material.
Embodiment 10
The difference from embodiment 1 is that heat treatment temperature is 900 DEG C in step (2), the sulphur that sulfur content is 3.68% is obtained
Adulterate hard carbon material.
Embodiment 11
(1) by sulfur content be 3.75% sulphur coal 1mol/L hydrochloric acid solution and 0.2mol/L hydrofluoric acid solution mixing
In solution after pickling for 24 hours, it is impregnated in 18h in alkaline solution, wherein aqueous slkali solute and the sulphur coal mass ratio after pickling are 2:
1, basic products are made after freeze-drying；
(2) by basic products with the heating rate of 1 DEG C/min to being heat-treated at a temperature of 700 DEG C, keep the temperature 3h, hard carbon be made
Material；
(3) hard carbon material is impregnated in the hydrochloric acid solution of 1mol/L for 24 hours, deionized water washing, filtering and 100 DEG C baking
It is dry, the sulfur doping hard carbon material that sulfur content is 3.28% is obtained, Fig. 3 is that the SEM of the hard carbon material schemes, as can be seen from the figure
Carbon is in pipe cell structure, and Fig. 4 is the XRD spectrum of the hard carbon material, and the hard carbon material is amorphous hard carbon as seen from the figure.
Embodiment 12
(1) sulphur coal that sulfur content is 4.27% after pickling 12h, is impregnated in alkaline solution in 1mol/L hydrochloric acid solution
Middle 12h, wherein aqueous slkali solute and the sulphur coal mass ratio after pickling are 1:1, and basic products are made after freeze-drying；
(2) by basic products with the heating rate of 5 DEG C/min to being heat-treated at a temperature of 800 DEG C, keep the temperature 6h, hard carbon be made
Material；
(3) hard carbon material is impregnated to 6h, deionized water washing, filtering and 80 DEG C of drying in the hydrochloric acid solution of 5mol/L,
Obtain the sulfur doping hard carbon material that sulfur content is 3.88%.
Embodiment 13
(1) sulphur coal that sulfur content is 4.27% after pickling 28h, is impregnated in alkaline solution in 1mol/L hydrochloric acid solution
Middle 28h, wherein aqueous slkali solute and the sulphur coal mass ratio after pickling are 1:1, and basic products are made after freeze-drying；
(2) by basic products with the heating rate of 0.5 DEG C/min to being heat-treated at a temperature of 800 DEG C, keep the temperature 1h, be made hard
Carbon material；
(3) hard carbon material is impregnated in the hydrochloric acid solution of 0.5mol/L for 24 hours, deionized water washing, filtering and 120 DEG C baking
It is dry, obtain the sulfur doping hard carbon material that sulfur content is 3.98%.
Comparative example 1
The difference from embodiment 1 is that sulphur coal is replaced with no sulphur coal.
Comparative example 2
The difference from embodiment 1 is that sulphur coal is replaced with no sulphur coal, basic products obtained are mixed to progress with sulphur powder
Heat treatment.
Performance test:
The N doping hard carbon material being prepared is performed the following performance tests:
(1) charge-discharge performance is tested, and the N doping hard carbon material being prepared is assembled into button battery, in 0.1A/g
Current density under, battery is tested for the property using blue electricity.
(2) Bet specific surface area is tested, and carries out specific surface area test using Bei Shide specific-surface area detection instrument.
Table 1
As can be seen from Table 1, kalium ion battery all has excellent cycle performance, the 200th coulomb in embodiment 1-13
Efficiency all reaches 99% or more.
It can be seen from Table 1 that embodiment 4 is poor relative to the chemical property of embodiment 1, it may be possible to due to being prepared into
To sulfur doping hard carbon material in sulfur content it is lower, the electro-chemical activity of material is lower, thus be made material chemical property
It is poor.
It can be seen from Table 1 that embodiment 7 is poor relative to the chemical property of embodiment 1, it may be possible to since NaOH contains
It measures lower, and then is difficult to generate big specific surface area, so the chemical property that material is made is poor.
It can be seen from Table 1 that embodiment 8 is poor relative to the chemical property of embodiment 1, it may be possible to since NaOH contains
Amount is higher, it is excessive that material micropore is made, and then pore structure is caused to be destroyed, and mechanical strength reduces, and electrode is easy in charge and discharge process
Dusting occurs, so the chemical property that material is made is poor.
It can be seen from Table 1 that comparative example 1 is poor relative to the chemical property of embodiment 1, it may be possible to due to comparative example
Not sulfur-bearing in 1 obtained material, the electro-chemical activity of material is lower, so the chemical property that material is made is poor.
It can be seen from Table 1 that comparative example 2 is poor relative to the chemical property of embodiment 1, it may be possible to due to comparative example
2 adulterate sulphur by the way of additional sulphur powder, and element sulphur is unevenly distributed and blocking duct easy to reunite, so the electrochemistry of material is made
Performance is poor.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of sulfur doping hard carbon material, which is characterized in that the hard carbon material has porous structure, the sulphur atom at least portion
It is distributed in the inside of the hard carbon material.
2. sulfur doping hard carbon material as described in claim 1, which is characterized in that in the hard carbon material sulfur content be 2~
10wt%；
Preferably, the hard carbon material has hierarchical porous structure；
It is further preferred that micropore, mesoporous and macropore is distributed in the hard carbon material；
Preferably, the pore-size distribution of the hard carbon material is 0.5nm~2 μm；
Preferably, the specific surface area of the hard carbon material is 280~1189m2/g。
3. a kind of preparation method of sulfur doping hard carbon material as claimed in claim 1 or 2, which is characterized in that the preparation side
Method includes the following steps:
(1) it by sulphur coal pickling, is then impregnated in alkaline solution, basic products is made；
(2) under protective atmosphere, basic products are heat-treated, hard carbon material is made.
4. preparation method as claimed in claim 3, which is characterized in that the sulfur content of the sulphur coal is 3~8wt%；
Preferably, the process of step (1) described pickling includes: to crush the sulphur coal, is impregnated in acid solution, is filtered, and is done
It is dry；
Preferably, the acid solution includes hydrochloric acid solution and/or hydrofluoric acid solution；
Preferably, the concentration of the hydrochloric acid solution is 0.5~5mol/L；
Preferably, the concentration of the hydroflouric acid solution is 0.1~1mol/L；
Preferably, the time of the pickling is 12~28h.
5. preparation method as described in claim 3 or 4, which is characterized in that solute and pickling in step (1) described alkaline solution
Sulphur coal mass ratio afterwards is 0.5:1~4:1；
Preferably, the alkaline solution includes KOH solution and/or NaOH solution；
Preferably, the time being impregnated in alkaline solution is 12~28h；
Preferably, the drying process is freeze-drying.
6. the preparation method as described in one of claim 3-5, which is characterized in that step (2) heat treatment temperature be 600~
900℃；
Preferably, the heating rate of the heat treatment is 0.5~5 DEG C/min；
Preferably, the time of the heat treatment is 1~6h；
Preferably, the protective atmosphere includes inert atmosphere, is preferably included in nitrogen atmosphere, argon atmosphere and helium atmosphere
Any one or at least two combination.
7. the preparation method as described in one of claim 3-6, which is characterized in that carry out step (3) after step (2): will be hard
Carbon material carries out acid solution immersion, washing, filtering and drying course；
Preferably, the acid solution includes hydrochloric acid solution and/or hydrofluoric acid solution；
Further preferably, the acid solution is hydrochloric acid solution；
Preferably, the concentration of the acid solution is 0.5~5mol/L；
Preferably, the time of the pickling be 6~for 24 hours；
Preferably, the washing includes that deionized water is washed；
Preferably, the temperature of the drying is 80~120 DEG C.
8. the preparation method of the sulfur doping hard carbon material as described in one of claim 3-7, which is characterized in that the preparation method
Include the following steps:
(1) by sulfur content be 3~8% sulphur coal in acid solution after 12~28h of pickling, be impregnated in 12 in alkaline solution~
28h, wherein aqueous slkali solute and the sulphur coal mass ratio after pickling are 0.5:1~4:1, and basic products are made after freeze-drying；
(2) by basic products with the heating rate of 0.5~5 DEG C/min to being heat-treated at a temperature of 600~900 DEG C, heat preservation 1~
Hard carbon material is made in 6h；
(3) hard carbon material impregnates to 6 in the hydrochloric acid solution of 0.5~5mol/L~for 24 hours, deionized water washing, filtering and 80~
120 DEG C of drying.
9. a kind of purposes of sulfur doping hard carbon material as claimed in claim 1 or 2, which is characterized in that the hard carbon material is used for
Field of batteries is preferred for kalium ion battery field；
Preferably, the hard carbon material is used as the negative electrode material of kalium ion battery.
10. a kind of kalium ion battery, which is characterized in that the kalium ion battery includes that sulfur doping of any of claims 1 or 2 is hard
Carbon material；
Preferably, the negative electrode material of the kalium ion battery includes sulfur doping hard carbon material of any of claims 1 or 2；
Preferably, the negative electrode material of the kalium ion battery is sulfur doping hard carbon material of any of claims 1 or 2.
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