CN108666571A - A kind of kalium ion battery negative material and preparation method thereof and cathode pole piece - Google Patents
A kind of kalium ion battery negative material and preparation method thereof and cathode pole piece Download PDFInfo
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- CN108666571A CN108666571A CN201710201533.XA CN201710201533A CN108666571A CN 108666571 A CN108666571 A CN 108666571A CN 201710201533 A CN201710201533 A CN 201710201533A CN 108666571 A CN108666571 A CN 108666571A
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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Abstract
The invention discloses a kind of kalium ion battery negative material and preparation method thereof and cathode pole pieces, negative material is graded porous carbon micro-sphere material and has graded porous structure, graded porous carbon micro-sphere material is made of the winding of N doping porous carbon nanofiber, the preparation method of potassium ion negative material is environmentally protective, it is simple for process, safety, it is of low cost and can include kalium ion battery negative material with mass, cathode pole piece.Negative material of the present invention has high-caliber N doping and graded porous structure simultaneously, both quick electronics and ion transmission ensure that, a large amount of interface storage potassium active site is provided simultaneously, enhance the adsorption capacity of potassium ion, there is prodigious facilitation to storage potassium specific capacity and high rate performance, high-energy density and the kalium ion battery negative material and cathode pole piece of high power density are provided.
Description
Technical field
The invention belongs to electrochemistry and battery technology fields, more particularly, to a kind of kalium ion battery negative material
And preparation method thereof and cathode pole piece.
Background technology
The energy and environment are two big eternal themes involved by human social.It is asked in face of the energy and environment
Topic, new cleaning fuel technology especially energy storage technology is considered as one of effective way.With traditional Ni-MH battery, plumbic acid electricity
Pond is compared, alkali metal ion (Li+/Na+/K+) battery is with higher energy density and environment friendly, in clean energy resource storage
Field has broad application prospects.Wherein lithium ion battery because its environment friendly, safety and high energy force density and length make
The advantages that with the service life, is widely used in the fields such as communication apparatus, electronic equipment and electric vehicle.But due to point of lithium resource
Cloth is uneven and reserves are less, and higher price is restricted in the application of extensive energy storage field.In comparison, sodium and potassium money
Source is very abundant, is widely present among the earth's crust and ocean, price is also cheaper.Also, sodium/potassium and lithium belong to same main group
Element, chemical property is close, and operation principle is similar.Therefore, sodium ion and kalium ion battery are considered as except lithium ion battery
Most promising alternative energy storage technology is especially led to the more demanding extensive energy storage of cost and resource abundance
Domain.
Sodium-ion battery is largely paid close attention to and is developed in recent years, positive cathode and associated batteries material all achieve compared with
Big progress.And as the kalium ion battery for being equally applicable to extensive energy storage field, the research being subject to is relatively fewer.It is several recently
Year achieves preferable progress about the research of potassium ion positive electrode both at home and abroad.And in terms of negative material, in recent years by more
Carry out more concerns.Wherein studying relatively broad has carbon based negative electrodes material.Carbon based negative electrodes material is mainly graphite, soft carbon and hard
Carbon material, specific capacity can be normally reached 200-300mAh g-1.But since potassium ion radius is larger, in graphite layers
Intercalation/deintercalation activity is not high, and high rate performance is poor.Hard carbon material is mostly non crystalline structure, stores up potassium high rate performance higher.But it is followed
Ring service life and high rate performance are still not ideal enough, still need further to be improved.
Ji etc. discloses one in non-patent literature (Advanced Energy Materials, 2016,6,1501874)
The kalium ion battery cathode of kind carbon based negative electrodes material, structure feature are indefinite form hard carbon material.However, due to its specific surface compared with
Low, storage potassium active site is less, and high rate performance and cycle life are all not ideal enough, and cycle-index is only capable of reaching 100, remote low
In the requirement of practical application.
Invention content
In view of the drawbacks of the prior art with existing actual specific capacity is relatively low, high rate performance is poor, cycle life is shorter
Problem, a kind of kalium ion battery negative material of present invention offer and preparation method thereof and cathode pole piece, its object is to can lead to
It crosses deintercalation mechanism and carries out storage potassium, and potassium mechanism can be stored up by interface and carry out storage potassium；Both conductive three-dimensional carbon network of fibers conduct
The quick transmission channel of electronics, ion, and there is big specific surface to provide a large amount of activity storage potassium potential point.Thus high-energy density is provided
With the kalium ion battery negative material of high power density.
To achieve the above object, according to one aspect of the present invention, a kind of kalium ion battery negative material is provided, is born
Pole material is graded porous carbon micro-sphere material and there is graded porous structure, graded porous structure to be conducive to the infiltration of electrolyte,
Promote the transmission of potassium ion.If without classifying porous micro-sphere structure, specific surface is relatively low, and activity storage potassium potential point is relatively low, and electrolyte
Infiltrate it is poor, storage potassium performance it is poor.
Graded porous carbon micro-sphere material is made of the winding of N doping porous carbon nanofiber.Nitrogen-doped carbon nano-fiber can carry
Highly electron conductive and adsorption capacity to potassium ion serve as interface storage potassium medium, improve electronic conductivity and adsorption to K+
Ability is with hoist capacity.
Further, nitrogen content is 1wt%-6wt%, the classifying porous carbosphere material in graded porous carbon micro-sphere material
The aperture of material be mesoporous and macropore, a diameter of 1 μm -50 μm of the graded porous carbon micro-sphere material.Classifying porous carbosphere material
The N doping of high-content not only increases the electric conductivity of carbon material in material, also improves its adsorption capacity to potassium ion.
Further, a diameter of 5 μm -50 μm of graded porous carbon micro-sphere material, aperture are 2nm-1 μm；The classification is more
Nitrogen content is 6wt% in the carbosphere material of hole, and the electrode cycle stability prepared at this time is also very excellent, and cycle life is up to
4000 times, 95% or more capacity retention ratio.
The second aspect according to the invention provides a kind of preparation method of kalium ion battery negative material, including
Following steps：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
6wt%-14wt%, urea account for the 2wt%-6wt% of mixed solution, and cryogenic temperature is that -20 DEG C to -45 DEG C holdings 2 hours -6 are small
When, several cycles of freeze-thaw are carried out, until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, -10
DEG C -0 DEG C stirs -2 hours 0.5 hour, obtains the second solution, wherein isooctane is solvent, and excessive isooctane is to ensure
First solution is dissolved completely in isooctane, and Span 85 is emulsifier, for constructing lotion, a small amount of Span 85 is added and makes
It is lotion to the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, and it is to remove isooctane and Span to carbosphere presoma be cleaned multiple times with second alcohol and water
85, third solution is freeze-dried -6 hours 2 hours at -20 DEG C to -45 DEG C and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in -4 hours 2 hours, at heat
It is 800 DEG C -1200 DEG C to manage temperature, obtains graded porous carbon micro-sphere material.
Preferably, chitin powder can improve kalium ion battery in this way by being obtained after the purified processing of natural chitin
With the nitrogen content of negative material.
In terms of third according to the invention, a kind of cathode pole piece of kalium ion battery is provided, which is characterized in that described
Cathode pole piece is uniformly mixed by kalium ion battery negative material, conductive agent and binder and coated on copper foil, through drying, cold
Pressure, punching are made.
Further, the quality of conductive agent is the 5%~10% of kalium ion battery negative material quality, the matter of binder
Amount is the 5%~10% of kalium ion battery negative material quality.
Further, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is potassium
For ion battery with the 10% of negative material quality, the battery cathode cyclical stability obtained at this time is also very excellent, recycles the longevity
Life is longer.
Further, binder is Kynoar, one kind in polytetrafluoroethylene (PTFE), the conductive agent be conductive carbon black,
One kind in electrically conductive graphite, Ketjen black, carbon nanotube.
Further, binder is Kynoar, and the conductive agent is acetylene black, and the battery cathode obtained at this time is followed
Ring stability is also very excellent, and cycle life is longer.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, have below beneficial to effect
Fruit：
(1) kalium ion battery is graded porous carbon micro-sphere material with negative material and has graded porous structure, classification more
The graded porous structure of hole carbosphere material forms abundant interfacial activity site after being conducive to electrolyte infiltration, is very beneficial for
Store up the progress of potassium in interface；
(2) graded porous carbon micro-sphere material is made of the winding of N doping porous carbon nanofiber, mutually the connected nitrogen of winding
Doped carbon nano-fiber is woven into three-dimensional network, provides continuous electronics, ion conduction channel；
(3) N doping of high-content not only increases the electric conductivity of carbon material in graded porous carbon micro-sphere material, also improves
Its adsorption capacity to potassium ion；Meanwhile this nanofiber be woven into microballoon structure it is highly stable, repeatedly store up K availability
After to remain to holding structure constant；
(4) present invention can not only improve the specific capacity and high rate performance of kalium ion battery negative material, it is ensured that
Its long-term cycle stability；
(5) preparation method of potassium ion negative material is environmentally protective, simple for process, safety, it is of low cost and can batch
Change；
(6) cathode pole piece of kalium ion battery have high-energy density and high power density, and with existing lithium-ion electric
Pond production line is mutually compatible with, and can directly use existing production line.
Description of the drawings
Fig. 1 is a kind of SEM figures of kalium ion battery negative material；
Fig. 2 is the SEM figures that Fig. 1 is further amplified；
Fig. 3 is a kind of TEM figures of kalium ion battery negative material；
Fig. 4 is a kind of XPS spectrum figure of kalium ion battery negative material；
Fig. 5 is a kind of CV curve graphs of the cathode pole piece of kalium ion battery；
Fig. 6 is a kind of high rate performance figure of the cathode pole piece of kalium ion battery；
Fig. 7 is the cycle performance comparison diagram of the embodiment of the present invention 1 and negative material in comparative example 1 and comparative example 2.
Specific implementation mode
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
It does not constitute a conflict with each other and can be combined with each other.
According to one aspect of the present invention, a kind of kalium ion battery negative material is provided, negative material is that classification is more
Hole carbosphere material and there is graded porous structure, graded porous structure is conducive to the infiltration of electrolyte, promotes the biography of potassium ion
It is defeated.If without classifying porous micro-sphere structure, specific surface is relatively low, and activity storage potassium potential point is relatively low, and electrolyte infiltration is poor, stores up potassium
It can be poor.
Graded porous carbon micro-sphere material is made of the winding of N doping porous carbon nanofiber.Nitrogen-doped carbon nano-fiber can carry
Highly electron conductive and adsorption capacity to potassium ion serve as interface storage potassium medium, consider and improve electronic conductivity and potassium
Ion adsorption capacity is with hoist capacity.
Further, nitrogen content is 1wt%-6wt%, the classifying porous carbosphere material in graded porous carbon micro-sphere material
The aperture of material be mesoporous and macropore, a diameter of 1 μm -50 μm of the graded porous carbon micro-sphere material.Classifying porous carbosphere material
The N doping of high-content not only increases the electric conductivity of carbon material in material, also improves its adsorption capacity to potassium ion.
Further, a diameter of 5 μm -50 μm of graded porous carbon micro-sphere material, aperture are 2nm-1 μm；The classification is more
Nitrogen content is 6wt% in the carbosphere material of hole, and the electrode cycle stability prepared at this time is also very excellent, and cycle life is up to
4000 times, 95% or more capacity retention ratio.
The second aspect according to the invention provides a kind of preparation method of kalium ion battery negative material, including
Following steps：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
6wt%-14wt%, urea account for the 2wt%-6wt% of mixed solution, and cryogenic temperature is that -20 DEG C to -45 DEG C holdings 2 hours -6 are small
When, several cycles of freeze-thaw are carried out, until obtaining the first transparent solution；
(2) the first solution is added in isooctane and the mixed solution of Span 85, wherein the first solution, isooctane and department
85 mass ratioes of class are 16: 40: 1, are stirred -2 hours 0.5 hour at -10 DEG C -0 DEG C, obtain the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried at -20 DEG C to -45 DEG C that obtain N doping within -6 hours 2 hours more to third solution
Hole carbon nano-fiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in -4 hours 2 hours, at heat
It is 800 DEG C -1200 DEG C to manage temperature, obtains graded porous carbon micro-sphere material.
Further, heat treatment temperature is higher, and carbosphere degree of graphitization is higher, and embedded type stores up potassium and contributes accounting more,
And capacitive storage potassium contributes accounting smaller.
Preferably, chitin powder can improve kalium ion battery in this way by being obtained after the purified processing of natural chitin
With the nitrogen content of negative material.
In terms of third according to the invention, a kind of cathode pole piece of kalium ion battery is provided, which is characterized in that described
Cathode pole piece is uniformly mixed simultaneously by kalium ion battery negative material, conductive agent and binder in N methyl pyrrolidone solvents
Coated on copper foil, it is made through drying, cold pressing, punching.
Further, the quality of conductive agent is the 5%~10% of kalium ion battery negative material quality, the matter of binder
Amount is the 5%~10% of kalium ion battery negative material quality.
Further, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is potassium
For ion battery with the 10% of negative material quality, the battery cathode cyclical stability obtained at this time is also very excellent, recycles the longevity
Life is longer.
Further, the thickness of cathode pole piece is 20-100 μm, a diameter of 0.8cm, the battery cathode cycle obtained at this time
Stability is also very excellent, and cycle life is longer.
Further, binder is Kynoar, one kind in polytetrafluoroethylene (PTFE), the conductive agent be conductive carbon black,
One kind in electrically conductive graphite, Ketjen black, carbon nanotube.
Further, binder is Kynoar, and the conductive agent is acetylene black, and the battery cathode obtained at this time is followed
Ring stability is also very excellent, and cycle life is longer.
Embodiment 1
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, wherein
First solution, isooctane and 85 mass ratio of Span are 16: 40: 1, are stirred 0.5 hour at 0 DEG C, obtain the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Comparative example 1
Kalium ion battery negative material, for the porous carbon microsphere of no N doping, preparation method and appearance structure and embodiment 1
In porous carbon microsphere it is similar, the chitin in step (1) is substituted by cellulose.Using the material directly as kalium ion battery
Electrode slice is made according to technique same as Example 1 in negative material.
Comparative example 2
Kalium ion battery negative material, is the carbosphere without porous structure of N doping, and preparation method is mixed with nitrogen in example 1
Miscellaneous porous carbon microsphere material is similar, only difference is that step (3) is without freeze-drying in preparation process, directly in an oven
80 DEG C of dryings (product obtained in this way is just without porous structure).Using the material as kalium ion battery negative material according to
Electrode slice is made in 1 identical technique of embodiment.
Analysis of experimental results
(1) morphology analysis
The kalium ion battery negative material that embodiment 1 obtains is dried after obtaining the powder of black, with SEM testers to sample
Product carry out morphology analysis, and the results are shown in Figure 1.It can be seen that 1 gained negative material of example is micro-sphere structure, microsphere diameter 5-50
Between micron.As shown in Fig. 2, discovery is further amplified, microballoon is interwoven by many nanofibers, is deposited between nanofiber
In gap.TEM figures show that nanofiber has porous structure in Fig. 3.So the kalium ion battery cathode material that the present invention obtains
Material is graded porous carbon micro-sphere material and has graded porous structure, and the graded porous carbon micro-sphere material is by N doping porous carbon
Nanofiber winding is constituted.
(2) amount of mixing is analyzed
Fig. 4 is the XPS figures of the kalium ion battery negative material in embodiment 1, it can be seen that the material contains the nitrogen of doping
Element, content are up to 6%, and most of is pyridine nitrogen.
(3) chemical property is analyzed
Fig. 5 is cyclic voltammetric (CV) curve graph that embodiment 1 obtains kalium ion battery cathode.It can be seen that not bright in figure
Aobvious oxidation/reduction peak shows the electrochemical characteristic based on capacitive character control storage potassium.In addition, having one in discharge process for the first time
A larger peak corresponds to the formation of solid electrolyte film in cyclic process for the first time.During following cycle, CV curves almost weigh
It closes, shows the good invertibity of electrode.
(4) electrode plates charge-discharge performance is analyzed
Fig. 6 is the high rate performance curve for the kalium ion battery cathode pole piece that embodiment 1 obtains, it can be seen that embodiment 1 makes
N doping porous carbon microsphere material has high specific discharge capacity, and~250mAh g are up under 0.12C multiplying powers-1(close to carbon
The storage potassium theoretical specific capacity 280mAh g of material-1), excellent high rate performance still has under the charge-discharge magnification of superelevation (72C)
More than 150mAh g-1Specific capacity.Fig. 7 is the cycle performance pair under 1.8C charge-discharge magnifications of embodiment 1 and comparative example 1,2
Than figure, it can be seen that the N doping porous carbon microsphere negative material that embodiment 1 uses is keeping high specific capacity (~180mAh
g-1) while, cyclical stability is also very excellent, and cycle life is up to 4000 times, 95% or more capacity retention ratio.
Table 1 is that the kalium ion battery specific capacity of embodiment 1 and comparative example 1,2 and cycle performance compare, wherein discharge capacity
The gross mass for being all based on all active materials is calculated.
The kalium ion battery specific capacity and cycle performance of table 1 embodiment 1 and comparative example 1,2
It is compared from the kalium ion battery specific capacity and cycle performance of embodiment 1 and comparative example 1,2 as can be seen that using this hair
Bright N doping porous carbon microsphere negative material, can be while ensureing that high power capacity plays, and effective raising electrode structure is steady
It is qualitative, so that kalium ion battery is obtained the cycle life of overlength.In addition, due to the N doping porous carbon microsphere cathode material in example 1
Expect while there is high-caliber N doping and graded porous structure, both ensure that quick electronics and ion transmission, provide simultaneously
Potassium active site is stored up at a large amount of interface, enhances the adsorption capacity of potassium ion, has to storage potassium specific capacity and high rate performance very big
Facilitation.
Embodiment 2
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
6wt%, urea account for the 6wt% of mixed solution, and cryogenic temperature is -20 DEG C, is kept for 6 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, -5
DEG C stirring 1 hour, obtain the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 6 hours at -20 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 1 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 2 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 3
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
14wt%, urea account for the 2wt% of mixed solution, and cryogenic temperature is -45 DEG C, is kept for 2 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, -10
DEG C stirring 0.5 hour, obtain the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 2 hours at -45 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, and binder is polytetrafluoroethylene (PTFE), and conductive agent is conductive stone
Ink, the quality of conductive agent are the 10% of kalium ion battery negative material quality, and the quality of binder is used for kalium ion battery to be born
The 5% of pole quality of materials.
Embodiment 3 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 4
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, and binder is Kynoar, and conductive agent is conductive stone
Ink, the quality of conductive agent are the 7% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 8% of quality of materials.
Embodiment 4 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 5
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 900 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 5 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 6
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 3 hours, heat treatment temperature
It is 1000 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 6 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 7
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 2 hours, heat treatment temperature
It is 1200 DEG C, obtains graded porous carbon micro-sphere material.
Obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classification
Porous carbon microsphere material and there is graded porous structure, graded porous carbon micro-sphere material winds by N doping porous carbon nanofiber
It constitutes, nitrogen content is 6wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, classification
A diameter of 5 μm -50 μm of porous carbon microsphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 7 has excellent high rate performance, cyclical stability using electrode made from kalium ion battery negative material
Also very excellent, cycle life is up to 4000 times, 95% or more capacity retention ratio.
Embodiment 8
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Further include cellulose in chitin powder in step (1), and the mass ratio of chitin and cellulose is 1: 3
When, obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classifying porous
Carbosphere material and have graded porous structure, graded porous carbon micro-sphere material by N doping porous carbon nanofiber wind structure
At nitrogen content is 1wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, and classification is more
A diameter of 5 μm -50 μm of hole carbosphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 8 has preferable high rate performance, stable circulation using electrode made from kalium ion battery negative material
Property also very good, 85% or more capacity retention ratio.
Embodiment 9
A kind of preparation method of kalium ion battery negative material, comprises the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for mixed solution
10wt%, urea account for the 4wt% of mixed solution, and cryogenic temperature is -30 DEG C, is kept for 4 hours, carries out several cycles of freeze-thaw,
Until obtaining the first transparent solution；
(2) the first solution is added in excessive isooctane and the mixed solution of a small amount of Span 85 and is sufficiently mixed, at 0 DEG C
Stirring 0.5 hour, obtains the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma carried out with second alcohol and water more
Secondary cleaning obtains third solution, is freeze-dried 4 hours at -30 DEG C to third solution and obtains N doping porous carbon nanofiber；
(4) above-mentioned N doping porous carbon nanofiber in a nitrogen atmosphere, carries out heat treatment in 4 hours, heat treatment temperature
It is 800 DEG C, obtains graded porous carbon micro-sphere material.
Further include cellulose in chitin powder in step (1), and the mass ratio of chitin and cellulose is 1: 1
When, obtained graded porous carbon micro-sphere material is the kalium ion battery negative material of the present invention, and negative material is classifying porous
Carbosphere material and have graded porous structure, graded porous carbon micro-sphere material by N doping porous carbon nanofiber wind structure
At nitrogen content is 3wt% in graded porous carbon micro-sphere material, and the aperture of graded porous carbon micro-sphere material is 2nm-1 μm, and classification is more
A diameter of 5 μm -50 μm of hole carbosphere material.
A kind of cathode pole piece of kalium ion battery, including kalium ion battery negative material, conductive agent and binder is equal
Even mixing is simultaneously coated on copper foil, is made through drying, cold pressing, punching, binder is Kynoar, and conductive agent is conductive carbon
Black, the quality of conductive agent is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery cathode
The 10% of quality of materials.
Embodiment 9 uses the high rate performance that electrode has had made from kalium ion battery negative material, cyclical stability
Also unusual good, 90% or more capacity retention ratio.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, all within the spirits and principles of the present invention made by all any modification, equivalent and improvement etc., should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of kalium ion battery negative material, which is characterized in that the negative material be graded porous carbon micro-sphere material and
With graded porous structure, the graded porous carbon micro-sphere material is made of the winding of N doping porous carbon nanofiber.
2. a kind of kalium ion battery negative material according to claim 1, which is characterized in that the graded porous carbon is micro-
Nitrogen content is 1wt%-6wt% in ball material, and the aperture of graded porous carbon micro-sphere material is mesoporous and macropore, described classifying porous
A diameter of 1 μm -50 μm of carbosphere material.
3. a kind of kalium ion battery negative material according to claim 1 or 2, which is characterized in that described classifying porous
A diameter of 5 μm -50 μm of carbosphere material, aperture are 2nm-1 μm；Nitrogen content is in the graded porous carbon micro-sphere material
6wt%.
4. a kind of preparation method of kalium ion battery negative material, which is characterized in that comprise the steps of：
(1) chitin powder is dispersed in the mixed solution of NaOH, urea and water, wherein NaOH accounts for the 6wt%- of mixed solution
14wt%, urea account for the 2wt%-6wt% of mixed solution, carry out several cycles of freeze-thaw, until it is molten to obtain transparent first
Liquid；
(2) the first solution is added in isooctane and the mixed solution of Span 85 and is sufficiently mixed, obtain the second solution；
(3) the second solution is centrifuged, obtains carbosphere presoma, carbosphere presoma clean with second alcohol and water
To third solution, third solution is freeze-dried to obtain N doping porous carbon nanofiber；
(4) in a nitrogen atmosphere, progress is thermally treated resulting in classifying porous carbosphere material to above-mentioned N doping porous carbon nanofiber
Material.
5. a kind of preparation method of kalium ion battery negative material according to claim 4, which is characterized in that the first
For shell element powder by being obtained after the purified processing of natural chitin, step (1) described cryogenic temperature is that -20 DEG C to -45 DEG C holdings 2 are small
When -6 hours, step (2) described reaction condition is to be stirred -2 hours 0.5 hour at -10 DEG C -0 DEG C, and step (3) freezing is dry
Dry condition is to be freeze-dried -6 hours 2 hours at -20 DEG C to -45 DEG C, and step (4) described heat treatment temperature is 800 DEG C -1200
DEG C, heat treatment time is -4 hours 2 hours.
6. a kind of cathode pole piece of kalium ion battery, which is characterized in that the cathode pole piece is by any one in claim 1-5
Kalium ion battery negative material, conductive agent and binder are uniformly mixed and coated on copper foil, are made through drying, cold pressing, punching
At.
7. a kind of cathode pole piece of kalium ion battery according to claim 6, which is characterized in that the quality of the conductive agent
It is the 5%~10% of kalium ion battery negative material quality, the quality of binder is kalium ion battery negative material quality
5%~10%.
8. a kind of cathode pole piece of kalium ion battery described according to claim 6 or 7, it is characterised in that the matter of the conductive agent
Amount is the 5% of kalium ion battery negative material quality, and the quality of binder is kalium ion battery negative material quality
10%.
9. a kind of cathode pole piece of kalium ion battery described according to claim 6 or 7, which is characterized in that the binder is
One kind in Kynoar, polytetrafluoroethylene (PTFE), the conductive agent are conductive carbon black, electrically conductive graphite, Ketjen black, acetylene black, carbon
One kind in nanotube.
10. a kind of cathode pole piece of kalium ion battery described according to claim 6 or 7, which is characterized in that the binder is
Kynoar, the conductive agent are acetylene black.
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| CN112794310A (en) * | 2020-12-30 | 2021-05-14 | 江苏大学 | Potassium ion battery negative electrode material and preparation method and application thereof |
| CN113697796A (en) * | 2021-07-09 | 2021-11-26 | 中山大学 | Three-dimensional communicated carbon nanosheet with ultrahigh specific surface area and preparation method and application thereof |
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| CN112794310B (en) * | 2020-12-30 | 2024-03-19 | 江苏大学 | Potassium ion battery anode material and preparation method and application thereof |
| CN113697796A (en) * | 2021-07-09 | 2021-11-26 | 中山大学 | Three-dimensional communicated carbon nanosheet with ultrahigh specific surface area and preparation method and application thereof |
| CN113697796B (en) * | 2021-07-09 | 2023-01-20 | 中山大学 | Three-dimensionally communicated carbon nanosheet with ultrahigh specific surface area, and preparation method and application thereof |
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