CN109301220A - A kind of N doping hard carbon material, preparation method and its kalium ion battery as cathode - Google Patents
A kind of N doping hard carbon material, preparation method and its kalium ion battery as cathode Download PDFInfo
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- CN109301220A CN109301220A CN201811179891.6A CN201811179891A CN109301220A CN 109301220 A CN109301220 A CN 109301220A CN 201811179891 A CN201811179891 A CN 201811179891A CN 109301220 A CN109301220 A CN 109301220A
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Abstract
The present invention relates to a kind of preparation method of N doping hard carbon material, the preparation method includes the following steps: that (1) is then impregnated in plant resources pickling in nitrogen source aqueous solution, and basic products are made；(2) under protective atmosphere, basic products are heat-treated, N doping hard carbon material is made.The N doping hard carbon material has porous structure, and nitrogen-atoms is distributed in inside the hard carbon material and surface, and nitrogen content is 1~10wt%, and specific surface area is less than 100m2/g.The N doping hard carbon material has the characteristics that capacity is high, coulombic efficiency is higher than 50%, good cycle for the first time and high rate performance is excellent, is used for kalium ion battery negative electrode material field, and preparation process is simple, and performance is controllable, has universality and can amplification.
Description
Technical field
The invention belongs to hard carbon material technical fields, and in particular to a kind of N doping hard carbon material, preparation method and its
As the kalium ion battery of cathode, the N doping hard carbon material is used for kalium ion battery field.
Background technique
Currently, lithium ion battery is by widespread commercial application, however, limited lithium resource has made lithium ion battery
Can not effectively meet the needs of power and extensive energy storage, in recent years, many novel substitution energy-storage batteries come into being simultaneously rapidly
Development mainly includes the secondary cells such as sodium ion, potassium ion, magnesium ion, calcium ion.
Kalium ion battery has many advantages, rich content, valence of the potassium resource in the earth's crust as novel substitution energy-storage battery
Lattice are cheap；Kalium ion battery and lithium ion battery redox potential are close；Have in organic electrolyte and compares Li+Higher ion
Conductivity；There is higher platform voltage etc. when using graphite as cathode.The research of kalium ion battery negative electrode material reported at present
Less, the emphasis of research still concentrates on carbon material especially hard carbon material.But hard carbon store up potassium mechanism and potassium ion compared with
Big size puts forward higher requirements cathode, the cellular structure of such as multistage distribution, biggish interlamellar spacing etc..
CN108358188A discloses a kind of secondary cell carbon negative pole material and preparation method thereof, by carbon source in protective atmosphere
Lower progress 2~40h of ball milling, obtains secondary cell carbon negative pole material.The carbon negative pole material has very big specific surface area and lacks
It falls into, but since specific surface area is larger, coulombic efficiency is poor for the first time.
CN107275578A discloses a kind of method that highly basic activation pomelo peel prepares three-dimensional carbon nanomaterial, by pomelo peel
It is freeze-dried after cleaning up, sulfuric acid solution is added and carries out hydro-thermal reaction, obtains biomass presoma, it then will be before biomass
It drives to be blended in tube-type atmosphere furnace after body washing suction filtration is dried with highly basic and be carbonized, obtain carbonized product, carbonized product is washed
It filters, obtains three-dimensional carbon nanomaterial after dry.The negative electrode material has the nanostructure of three-dimensional porous connection, has larger
Specific surface area, but the material aperture is smaller, is not able to satisfy that kalium ion battery is embedding/de- to be required.
CN107331867A discloses a kind of nitrogen-doped porous carbon material preparation side as anode material of lithium-ion battery
Method belongs to the preparation method of N doping porous carbon.By means of simple and easy high-temperature solid phase reaction method, by regulating and controlling reaction process
In each parameter, realize and the control of nitrogen-doped carbon material synthesized, and anode material of lithium-ion battery is made into its application.The nitrogen is mixed
The synthetic method of miscellaneous porous carbon materials is simple, and operating procedure controllability is high, and is easily enlarged production, but the material aperture compared with
It is small, it is not able to satisfy kalium ion battery and take off/inlays requirement.
So this field needs to develop a kind of carbon negative pole material for kalium ion battery, it is more to make it have stable classification
Pore structure, specific capacity is big, good cycling stability, and coulombic efficiency is high for the first time, 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 preparation sides of N doping hard carbon material
Method includes the following steps:
(1) it by plant resources pickling, is then impregnated in nitrogen source aqueous solution, basic products is made；
(2) under protective atmosphere, basic products are heat-treated, N doping hard carbon material is made.
The present invention utilizes the pattern and structure of plant itself, passes through heat treatment item of the control plant into hard carbon conversion process
Part makes carbon material obtained inherit the graded multi-hole shape structure of plant itself.Simultaneously as constituting the fibre structure of cell wall
In there are a large amount of oxygen atom, in carbonisation carbon atom hexagonal annulus at layer structure it is messy and irregular, and then shape
The defects of at a large amount of holes and edge, is conducive to the absorption and storage of potassium ion.
The present invention can regulate and control the interlamellar spacing of carbon material by control heat treatment condition, be conducive to improve potassium ion in stone
Diffusion in layer of ink, to improve storage potassium performance.
Carbon negative pole material prepared by the present invention, centre does not have activation process, therefore the specific surface area of carbon material is in 100m2/g
Within, to there is higher coulombic efficiency for the first time.
The present invention carries out attached nitrogen process, nitrogen-atoms and carbon atom atomic radius by impregnating plant in nitrogen source aqueous solution
It is similar, but the electronegativity of nitrogen-atoms and carbon atom differs greatly, and after nitrogen-atoms enters carbon base body, it is original to change carbon lattice
Cloud density distribution, and then improve the mutual of material electronics conductivity and surface wettability, charge migration and electrode/electrolyte
Effect and increase defect active site, promote carbon material and store up potassium performance.
Preferably, step (2) the of the present invention heat treatment the specific steps are after room temperature temperature programming to predetermined temperature
Carry out isothermal holding.
Preferably, the predetermined temperature be 700~1200 DEG C, such as 750 DEG C, 800 DEG C, 850 DEG C, 900 DEG C, 950 DEG C,
1000 DEG C, 1100 DEG C etc..
Preferably, described program heating heating rate≤2 DEG C/min, such as 0.1 DEG C/min, 0.3 DEG C/min, 0.5 DEG C/
Min, 1 DEG C/min, 1.2 DEG C/min, 1.5 DEG C/min, 1.8 DEG C/min etc..
Preferably, the time of the isothermal holding≤3h, such as 0.5h, 1h, 1.5h, 2h, 2.5h etc..
Preferably, step (1) the of the present invention plant resources include plant waste.
Preferably, the plant resources include in walnut Diaphragma juglandis stalk, maize peel, peanut skin and willow leaf any one or
At least two combination, such as walnut Diaphragma juglandis stalk, maize peel, peanut skin etc..
Pattern and structure to plant resources carry out that preferably, more reasonable pore-size distribution can be obtained, and are made and are more suitable for potassium
The classification cavernous structure of ion battery.
Preferably, the process of step (1) the of the present invention pickling includes: that the plant waste is impregnated in acid solution
In, it filters, it is dry.
Preferably, the concentration of the acid solution be 0.5~5mol/L, such as 1mol/L, 1.5mol/L, 2mol/L,
2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L etc..
Preferably, the time of the pickling is 12~26h, such as 15h, 18h, 20h, 22h, for 24 hours etc..
Preferably, the acid solution includes hydrochloric acid solution, and preferred concentration is the hydrochloric acid solution of 0.5~5mol/L.
Preferably, the nitrogen source aqueous solution includes any one in aqueous solution of urea, melamine aqueous solution and ammonium hydroxide
Or at least two combination.
Preferably, the mass ratio of the nitrogen source and plant waste be 0.1~2:1, such as 0.2:1,0.5:1,0.8:1,
1:1,1.2:1,1.5:1,1.8:1 etc..
Preferably, step (1) dip time being impregnated in nitrogen source aqueous solution be 8~for 24 hours, such as 10h, 12h,
16h, 18h, 20h, 22h etc..
Preferably, the mode of the drying includes freeze-drying.
Preferably, step (2) the of the present invention protective atmosphere includes inert atmosphere, preferably includes nitrogen atmosphere, argon gas
Any one or at least two combination, such as argon atmosphere, helium atmosphere etc. in atmosphere and helium atmosphere.
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.
Preferably, the concentration of the acid solution be 0.5~5mol/L, such as 1mol/L, 1.5mol/L, 2mol/L,
2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L etc..
Preferably, the time of the pickling be 8~for 24 hours, such as 10h, 12h, 16h, 18h, 20h, 22h etc..
Preferably, the washing includes that deionized water is washed.
Preferably, the temperature of the drying is 80~120 DEG C, such as 90 DEG C, 100 DEG C, 110 DEG C etc..
As optimal technical scheme, the preparation method of N doping hard carbon material of the present invention, the preparation method packet
Include following steps:
(1) plant waste is impregnated in 12~26h of pickling in the hydrochloric acid solution of 0.5~5mol/L, is then impregnated in nitrogen
8 in the aqueous solution of source~for 24 hours, wherein the mass ratio of nitrogen source and plant waste is 0.1~2:1, freeze-drying in nitrogen source aqueous solution
Basic products are made afterwards；
(2) basic products are risen at a temperature of 700~1200 DEG C with heating rate≤2 DEG C/min and is heat-treated, when heat preservation
Between≤3h, hard carbon material is made；
(3) hard carbon material impregnates to 8 in the hydrochloric acid solution of 0.5~5mol/L~for 24 hours, deionized water washing, filtering and
80~120 DEG C of drying, obtain N doping hard carbon material.
The second object of the present invention is to provide a kind of N doping hard carbon material, the hard carbon material passes through described in the first purpose
Method be prepared.
Preferably, the hard carbon material has porous structure, and nitrogen-atoms is distributed in the hard carbon material surface and inside.
Preferably, in the hard carbon material nitrogen content be 1~10wt%, such as 2wt%, 4wt%, 5wt%, 7wt%,
8wt%, 9wt% etc..
Preferably, the hard carbon material has hierarchical porous structure.
Preferably, micropore, mesoporous and macropore is distributed in the hard carbon material.
Preferably, the pore-size distribution of the hard carbon material be 2nm~6 μm, such as 5nm, 10nm, 100nm, 500nm, 1 μm,
2 μm, 4 μm, 5 μm etc..
Preferably, the specific surface area of the hard carbon material is 10m2/ g~100m2/ g, such as 20m2/g、30m2/g、40m2/
g、50m2/g、70m2/g、90m2/ g etc..
Preferably, the interlamellar spacing of the hard carbon material be 0.354~0.395nm, such as 0.358nm, 0.364nm,
0.375nm, 0.382nm, 0.390nm, 0.393nm etc..
The porous carbon materials that the present invention designs are three-dimensional graded porous structure, can match kalium ion battery to negative electrode material
Requirement, the doping of nitrogen-atoms can change carbon lattice original cloud density distribution, assign material new electro-chemical activity, full
Sufficient potassium ion intercalation/deintercalation requirement.
The hard carbon material that the present invention designs keeps the pattern and skeleton structure of former vegetable material, has good machinery
Performance and lesser specific surface area assign the good cyclical stability of N doping hard carbon material, and coulombic efficiency is more than for the first time
50%, coulombic efficiency >=99.5% after recycling 200 times.
The three of the object of the invention are to provide a kind of purposes of N doping hard carbon material as described in the second 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 is mixed with nitrogen described in the second purpose
Miscellaneous hard carbon material is as cathode.
Preferably, the negative electrode material of the kalium ion battery is using N doping hard carbon material described in the second purpose as negative
Pole.
Compared with prior art, the invention has the following beneficial effects:
(1) heat treatment condition of the present invention by control plant into hard carbon conversion process protects hard carbon material obtained
The eucaryotic cell structure of plant is held, and the defects of there are a large amount of holes and edges, and material interlamellar spacing is big, is conducive to the expansion of potassium ion
It dissipates, adsorb and stores.
(2) in the N doping hard carbon material that the present invention designs, the doping of nitrogen-atoms can change the original electron cloud of carbon lattice
Density Distribution, so improve material electronics conductivity and surface wettability, charge migration and electrode/electrolyte interaction,
And increase defect active site, it promotes carbon material and stores up potassium performance.
(3) hard carbon material that present invention design obtains keeps the pattern and skeleton structure of former vegetable material, for three-dimensional classification
Porous structure has good mechanical performance, assigns the good cyclical stability of N doping hard carbon material, recycles 200 times
Coulombic efficiency >=99.5% afterwards.
(4) hard carbon material that present invention design obtains has lesser specific surface area, and coulombic efficiency is all larger than 50% for the first time,
It realizes and stores up potassium compared with height ratio capacity under low specific surface area.
Detailed description of the invention
Fig. 1 is the resulting N doping hard carbon material SEM of embodiment 1 figure；
Fig. 2 is the resulting N doping hard carbon material XRD spectrum of embodiment 1；
Fig. 3 is the resulting N doping hard carbon material SEM of embodiment 12 figure；
Fig. 4 is the resulting N doping hard carbon material XRD spectrum of embodiment 12；
Fig. 5 is the resulting N doping hard carbon material SEM of embodiment 13 figure；
Fig. 6 is the resulting N doping hard carbon material XRD spectrum of embodiment 13；
Fig. 7 is the resulting N doping hard carbon material SEM of embodiment 14 figure；
Fig. 8 is the resulting N doping hard carbon material XRD spectrum of embodiment 14；
Fig. 9 is the resulting N doping hard carbon material SEM of embodiment 15 figure；
Figure 10 is the resulting N doping hard carbon material XRD spectrum of embodiment 15.
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
A kind of preparation method of N doping hard carbon material includes the following steps:
(1) walnut Diaphragma juglandis pickling in the hydrochloric acid solution of 1mol/L is impregnated in for 24 hours, to be then impregnated in aqueous solution of urea
12h, wherein the mass ratio of urea and walnut Diaphragma juglandis is 1:1 in aqueous solution of urea, and basic products are made after freeze-drying；
(2) basic products are risen at a temperature of 800 DEG C with 0.5 DEG C/min heating rate and is heat-treated, heat preservation 2h is made hard
Carbon 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 1mol/L
Dry, the nitrogen content that N doping hard carbon material is made is 6.56%.The pattern of the N doping hard carbon material is as shown in Figure 1, in figure
The hard carbon material be can be seen that in honeycomb structure, pore-size distribution is 2nm~2 μm, specific surface area 55.3m2/ g, interlamellar spacing are
0.376nm.Fig. 2 is the XRD spectrum of the hard carbon material, and the carbon material is amorphous hard carbon as seen from the figure.
Embodiment 2
The difference from embodiment 1 is that the mass ratio of urea and plant waste is in aqueous solution of urea in step (1)
0.1:1, the nitrogen content that N doping hard carbon material is made is 1.0%, specific surface area 57.2m2/ g, interlamellar spacing 0.395nm.
Embodiment 3
The difference from embodiment 1 is that the mass ratio of urea and plant waste is 2 in aqueous solution of urea in step (1):
1, the nitrogen content that N doping hard carbon material is made is 6.75%, specific surface area 52.1m2/ g, interlamellar spacing 0.354nm.
Embodiment 4
The difference from embodiment 1 is that the mass ratio of urea and plant waste is in aqueous solution of urea in step (1)
The nitrogen content that N doping hard carbon material is made in 0.05:1 is 0.5%, specific surface area 56.8m2/ g, interlamellar spacing 0.396nm.
Embodiment 5
The difference from embodiment 1 is that the mass ratio of urea and plant waste is 3 in aqueous solution of urea in step (1):
1, the nitrogen content that N doping hard carbon material is made is 6.74%, specific surface area 48.6m2/ g, interlamellar spacing 0.348nm.
Embodiment 6
The difference from embodiment 1 is that heating rate is 2 DEG C/min in step (2), the nitrogen of N doping hard carbon material is made
Content is 6.48%, specific surface area 50.2m2/ g, interlamellar spacing 0.378nm.
Embodiment 7
The difference from embodiment 1 is that heating rate is 3 DEG C/min in step (2), the nitrogen of N doping hard carbon material is made
Content is 6.55%, specific surface area 38.6m2/ g, interlamellar spacing 0.382nm.
Embodiment 8
The difference from embodiment 1 is that soaking time is 3h in step (2), the nitrogen content of N doping hard carbon material is made
It is 6.44%, specific surface area 52.3m2/ g, interlamellar spacing 0.377nm.
Embodiment 9
The difference from embodiment 1 is that soaking time is 4h in step (2), the nitrogen content of N doping hard carbon material is made
It is 6.34%, specific surface area 53.1m2/ g, interlamellar spacing 0.380nm.
Embodiment 10
The difference from embodiment 1 is that heat treatment temperature is 700 DEG C in step (2), the nitrogen of N doping hard carbon material is made
Content is 6.64m2/ g, specific surface area 57.8m2/ g, interlamellar spacing 0.396nm.
Embodiment 11
The difference from embodiment 1 is that heat treatment temperature is 1200 DEG C in step (2), N doping hard carbon material is made
Nitrogen content is 6.01%, specific surface area 20.1m2/ g, interlamellar spacing 0.346nm.
Embodiment 12
A kind of preparation method of N doping hard carbon material includes the following steps:
(1) maize peel is impregnated in pickling 26h in the hydrochloric acid solution of 0.5mol/L, be then impregnated in aqueous solution of urea
For 24 hours, wherein the mass ratio of urea and maize peel is 0.1:1 in aqueous solution of urea, and basic products are made after freeze-drying；
(2) basic products are risen at a temperature of 700 DEG C with 1 DEG C/min heating rate and is heat-treated, hard carbon is made in heat preservation 2h
Material；
(3) hard carbon material is impregnated to 18h, deionized water washing, filtering and 110 DEG C of bakings in the hydrochloric acid solution of 1mol/L
Dry, the nitrogen content that N doping hard carbon material is made is 1.1%.The pattern of the N doping hard carbon material is as shown in figure 3, can in figure
The hard carbon material is found out in honeycomb structure, and pore-size distribution is 2nm~4 μm, specific surface area 48.7m2/ g, interlamellar spacing are
0.391nm, Fig. 4 are the XRD spectrum of the hard carbon material, and the carbon material is amorphous hard carbon as seen from the figure.
Embodiment 13
A kind of preparation method of N doping hard carbon material includes the following steps:
(1) peanut skin is impregnated in pickling 16h in the hydrochloric acid solution of 2.5mol/L, be then impregnated in aqueous solution of urea
8h, wherein the mass ratio of urea and peanut skin is 3:5 in aqueous solution of urea, and basic products are made after freeze-drying；
(2) basic products are risen at a temperature of 1000 DEG C with 2 DEG C/min heating rate and is heat-treated, hard carbon is made in heat preservation 3h
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, the nitrogen content that N doping hard carbon material is made is 4.38%.The pattern of the N doping hard carbon material is as shown in figure 5, in figure
It can be seen that the hard carbon material in Lotus-type Structure, specific surface area 32.4m2/ g, interlamellar spacing 0.361nm, Fig. 6 are the hard carbon
The XRD spectrum of material, the carbon material is amorphous hard carbon as seen from the figure.
Embodiment 14
A kind of preparation method of N doping hard carbon material includes the following steps:
(1) maize peel is impregnated in pickling 12h in the hydrochloric acid solution of 3mol/L, be then impregnated in melamine aqueous solution
For 24 hours, wherein the mass ratio of melamine and maize peel is 1:1 in melamine aqueous solution, and basic products are made after freeze-drying；
(2) basic products are risen at a temperature of 1100 DEG C with 0.5 DEG C/min heating rate and is heat-treated, heat preservation 3h is made hard
Carbon material；
(3) hard carbon material is impregnated in the hydrochloric acid solution of 1mol/L for 24 hours, deionized water washing, filtering and 80 DEG C drying,
The nitrogen content that N doping hard carbon material is made is 5.52%.The pattern of the N doping hard carbon material in figure as shown in fig. 7, can see
The hard carbon material is in chop shape structure out, and pore-size distribution is 2nm~4 μm, specific surface area 40.2m2/ g, interlamellar spacing are
0.358nm, Fig. 8 are the XRD spectrum of the hard carbon material, and the carbon material is amorphous hard carbon as seen from the figure.
Embodiment 15
A kind of preparation method of N doping hard carbon material includes the following steps:
(1) peanut skin is impregnated in pickling 12h in the hydrochloric acid solution of 5mol/L, be then impregnated in melamine aqueous solution
8h, wherein the mass ratio of melamine and peanut skin is 2:1 in melamine aqueous solution, and basic products are made after freeze-drying；
(2) basic products are risen at a temperature of 1200 DEG C with 2 DEG C/min heating rate and is heat-treated, hard carbon is made in heat preservation 2h
Material；
(3) hard carbon material is impregnated to 8h, deionized water washing, filtering and 120 DEG C of drying in the hydrochloric acid solution of 5mol/L,
The nitrogen content that N doping hard carbon material is made is 6.31%.The pattern of the N doping hard carbon material in figure as shown in figure 9, can see
The hard carbon material is in Lotus-type Structure, specific surface area 30.6m out2/ g, interlamellar spacing 0.350nm, Figure 10 are the hard carbon material
The XRD spectrum of material, the carbon material is amorphous hard carbon as seen from the figure.
Comparative example 1
The difference from embodiment 1 is that not adding urea in step (1).
Comparative example 2
The difference from embodiment 1 is that plant waste replaces with pitch in step (1).
Performance test:
The N doping hard carbon material being prepared is subjected to charge-discharge performance test:
Table 1
As can be seen from Table 1, kalium ion battery all has excellent coulombic efficiency for the first time and cyclicity in embodiment 1-15
Can, coulombic efficiency all reaches 50% or more for the first time, and the 200th time coulombic 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 N doping hard carbon material in nitrogen 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 due to heating speed
Rate is very fast, causes the destruction of material internal structure, so the chemical property that material is made is poor.
It can be seen from Table 1 that embodiment 9 is poor relative to the chemical property of embodiment 1, it may be possible to when due to heat preservation
Between it is longer, and then nitrogen content is relatively low in N doping hard carbon material, 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 nitrogenous 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
The defects of interlamellar spacing is smaller in hard carbon material made from 2 and hole and edge is less, and the absorption and storage for being unsatisfactory for potassium ion are wanted
It asks.
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 preparation method of N doping hard carbon material, which is characterized in that the preparation method includes the following steps:
(1) it by plant resources pickling, is then impregnated in nitrogen source aqueous solution, basic products is made；
(2) under protective atmosphere, basic products are heat-treated, N doping hard carbon material is made.
2. preparation method as described in claim 1, which is characterized in that step (2) described heat treatment the specific steps are from room
Isothermal holding is carried out after warm temperature programming to predetermined temperature；
Preferably, the predetermined temperature is 700~1200 DEG C；
Preferably, heating rate≤2 DEG C/min of described program heating；
Preferably, the time of the isothermal holding≤3h.
3. preparation method as claimed in claim 1 or 2, which is characterized in that step (1) described plant resources include plant waste
Object；
Preferably, the plant resources include in walnut Diaphragma juglandis stalk, maize peel, peanut skin and willow leaf any one or at least
Two kinds of combination.
4. the preparation method as described in one of claim 1-3, which is characterized in that the process of step (1) described pickling include: by
The plant waste is impregnated in acid solution, is filtered, dry；
Preferably, the concentration of the acid solution is 0.5~5mol/L；
Preferably, the time of the pickling is 12~26h；
Preferably, the acid solution includes hydrochloric acid solution, and preferred concentration is the hydrochloric acid solution of 0.5~5mol/L；
Preferably, the nitrogen source aqueous solution include in aqueous solution of urea, melamine aqueous solution and ammonium hydroxide any one or extremely
Few two kinds of combination；
Preferably, the mass ratio of the nitrogen source and plant waste is 0.1~2:1；
Preferably, step (1) dip time being impregnated in nitrogen source aqueous solution be 8~for 24 hours；
Preferably, the mode of the drying includes freeze-drying.
5. the preparation method as described in one of claim 1-4, which is characterized in that step (2) described protective atmosphere includes lazy
Property atmosphere, preferably include in nitrogen atmosphere, argon atmosphere and helium atmosphere any one or at least two combination.
6. the preparation method as described in one of claim 1-5, 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；
Preferably, the concentration of the acid solution is 0.5~5mol/L；
Preferably, the time of the pickling be 8~for 24 hours；
Preferably, the washing includes that deionized water is washed；
Preferably, the temperature of the drying is 80~120 DEG C.
7. the preparation method of N doping hard carbon material as described in one of claim 1-6, which is characterized in that the preparation method packet
Include following steps:
(1) plant waste is impregnated in 12~26h of pickling in the hydrochloric acid solution of 0.5~5mol/L, is then impregnated in nitrogen source water
8 in solution~for 24 hours, wherein the mass ratio of nitrogen source and plant waste is 0.1~2:1 in nitrogen source aqueous solution, is made after freeze-drying
Obtain basic products；
(2) basic products are risen at a temperature of 700~1200 DEG C with heating rate≤2 DEG C/min and is heat-treated, soaking time≤
Hard carbon material is made in 3h；
(3) hard carbon material impregnates to 8 in the hydrochloric acid solution of 0.5~5mol/L~for 24 hours, deionized water washing, filtering and 80~
120 DEG C of drying, obtain N doping hard carbon material.
8. a kind of N doping hard carbon material that the preparation method of the N doping hard carbon material as described in one of claim 1-7 obtains
Material, which is characterized in that the hard carbon material has porous structure, and nitrogen-atoms is distributed in the hard carbon material surface and inside；
Preferably, nitrogen content is 1~10wt% in the hard carbon material；
Preferably, the hard carbon material has hierarchical porous structure；
Preferably, micropore, mesoporous and macropore is distributed in the hard carbon material；
Preferably, the pore-size distribution of the hard carbon material is 2nm~6 μm；
Preferably, the specific surface area of the hard carbon material is 10m2/ g~100m2/g；
Preferably, the interlamellar spacing of the hard carbon material is 0.354~0.395nm.
9. a kind of purposes of N doping hard carbon material as claimed in claim 8, which is characterized in that the hard carbon material is used for battery
Field 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 N doping hard carbon according to any one of claims 8
Material；
Preferably, the negative electrode material of the kalium ion battery includes N doping hard carbon material according to any one of claims 8；
Preferably, the negative electrode material of the kalium ion battery is N doping hard carbon material according to any one of claims 8.
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| CN114715875A (en) * | 2022-03-31 | 2022-07-08 | 宁波大学 | Preparation method of thin-layer carbon-based material and application of thin-layer carbon-based material as battery material |
| CN114604851A (en) * | 2022-04-12 | 2022-06-10 | 广州碳加科技有限公司 | Preparation method of porous carbon for producing carbon molecular sieve |
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