CN109244393A - A kind of lithium sulfur battery anode material and preparation method thereof of long circulating high rate capability - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof of long circulating high rate capability Download PDFInfo
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- CN109244393A CN109244393A CN201810982290.2A CN201810982290A CN109244393A CN 109244393 A CN109244393 A CN 109244393A CN 201810982290 A CN201810982290 A CN 201810982290A CN 109244393 A CN109244393 A CN 109244393A
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Abstract
The present invention relates to a kind of lithium sulfur battery anode materials and preparation method thereof of long circulating high rate capability, the following steps are included: (1) nickel salt solution is added in water suction macromolecule resin, under constant temperature, uniformly mixed oscillation obtains hydrogel, xerogel presoma will be obtained after obtained hydrogel cryogenic freezing, drying, after xerogel presoma is carried out high-temperature calcination again, cooling obtains thermal decomposition product；(2) after thermal decomposition product being mixed to immersion with hydrofluoric acid, washing to neutrality, drying obtains hollow nano-graphite carbon ball；(3) it by hollow nano-graphite carbon ball and elemental sulfur mixed grinding, adds after carbon disulfide continues grinding, drying obtains hollow nano-graphite carbon ball compounding simple-substance sulfur materials in closed container.Compared with prior art, lithium sulfur battery anode material prepared by the present invention charging and discharging capacity with higher, excellent cyclical stability and good high rate performance, method is simple, low in cost, has excellent performance, the production suitable for large-scale commercial applications battery.
Description
Technical field
The present invention relates to a kind of lithium sulfur battery anode materials, more particularly, to a kind of lithium sulphur electricity of long circulating high rate capability
Pond positive electrode and preparation method thereof.
Background technique
Lithium-sulfur cell energy storage principle is the fracture of sulphur-sulfide linkage and lives again that active material is sulphur.Elemental sulfur is main at normal temperature
With S8Form exist, the rich reserves in the earth have the characteristics that cheap, environmental-friendly.Using sulphur as positive material
The lithium-sulfur cell of material, materials theory specific capacity and battery theory specific energy are higher, respectively reach 1672mAhg-1With
2600Wh·kg-1.It is considered as one of the lithium secondary battery system of present most researching value and application prospect.Although lithium sulphur
Battery has many advantages, such as high capacity, high-energy-density, but there is that active material utilization is low, cycle life is low and peace at present
The problems such as property is poor entirely, this seriously restricts the development of lithium-sulfur cell.The main reason for causing the above problem has the following aspects:
1) elemental sulfur is electronics and ion insulator, and room-temperature conductivity is low, since the sulphur of not no ionic state exists, thus is made
Difficulty is activated for positive electrode, leads to lithium-sulfur cell low range performance issue；
2) the poly- more lithium sulfide Li of state of height generated in electrode process2Sn(8 > n > 4) are soluble in electrolyte, just
Concentration difference is formed between cathode, cathode is moved under the action of concentration gradient, and the high poly- more lithium sulfides of state are reduced by lithium metal
The oligomeric more lithium sulfides of state.With the progress reacted above, the oligomeric more lithium sulfides of state are assembled in cathode, finally shape between electrodes
At concentration difference, and moves to anode and be oxidized to the high poly- more lithium sulfides of state.This phenomenon is referred to as shuttle effect, and it is living to reduce sulphur
The utilization rate of property substance.Insoluble Li simultaneously2S and Li2S2It is deposited on cathode of lithium surface, is further degrading lithium-sulfur cell
Performance, lead to the low circulation performance issue of lithium-sulfur cell；
3) sulphur and final product Li2The density of S is different, and volume expansion about 79%, easily leads to Li after sulphur is lithiated2S's
Dusting causes the safety problem of lithium-sulfur cell.
Summary of the invention
It is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of long circulating high magnifications
Lithium sulfur battery anode material of performance and preparation method thereof.
The present invention absorbs aqueous metal salt by the hydroscopic high-molecular resin with macromolecule solid network binding structure, then
Hydrogel is formed, ice gel is converted by hydrogel, obtains xerogel presoma finally by freeze-drying, then pass through high temperature
Calcining, obtains hollow nano-graphite carbon ball after pickling, be loaded into elemental sulfur in hollow nano graphite carbon finally by the method for melting
Hollow nano-graphite carbon ball compounding simple-substance sulfur materials are obtained after in ball.
Technical principle of the invention:
The absorbent polymer resin used in the present invention, direct carbonization can only obtain unordered hard carbon nanometer chip architecture,
But after absorbent polymer absorbs acetic acid nickel salt solution, nickel is dispersed in polymeric particles in the form of an ion, rear
Nickel ion makes unordered hard carbon nanometer sheet be rearranged into orderly graphitic carbon during continuous high temperature cabonization, and surrounds metallic nickel
Form nano-graphite carbon ball.Finally with obtaining hollow nano-graphite carbon ball after acid etch.This structure be conducive to store sulphur and
The shuttle effect for inhibiting polysulfide, to obtain macrocyclic powerful lithium sulfur battery anode material.
Technical solution of the present invention:
A kind of lithium sulfur battery anode material of long circulating high rate capability, the material are the hollow compound list of nano-graphite carbon ball
Matter sulphur.Preparation method the following steps are included:
(1) nickel salt solution is added in water suction macromolecule resin, uniformly mixed oscillation obtains hydrogel, the water-setting that will be obtained
After glue cryogenic freezing, drying, xerogel presoma is obtained, then by after the progress high-temperature calcination of xerogel presoma, cooling obtains heat
Solve product；
(2) after the thermal decomposition product that step (1) obtains being mixed immersion with hydrofluoric acid, washing to neutrality, drying obtains hollow
Nano-graphite carbon ball；
(3) the hollow nano-graphite carbon ball for obtaining step (2) and elemental sulfur mixed grinding add carbon disulfide continuation
After grinding, drying obtains hollow nano-graphite carbon ball compounding simple-substance sulfur materials in closed container.
As a preferred embodiment of the above technical solution, in step (1): the nickel salt is nickel acetate, the superabsorbent water high score subtree
Rouge is Sodium Polyacrylate (coming from baby's diaper), and the mass ratio of nickel salt and superabsorbent water macromolecule resin is 1:1-1:100.At this
Regulation mass ratio can preferably grow graphite carbon ball in one range.Nickel salt quality is very few, will be unable to be catalyzed in carbonisation
All hard carbon nanometer sheets are rearranged into graphite carbon ball, and nickel salt quality is excessive, and the carbon shell defect that will lead to graphite carbon ball is excessive,
All have an impact to pattern and performance.
As a preferred embodiment of the above technical solution, in step (1), the mixed process of nickel salt solution and water suction macromolecule resin is
Constant temperature handles 30min-24h in 10-50 DEG C.Constant temperature processing during this is conducive to absorbent polymer and inhales nickel salt solution
It receives sufficiently, to be hardly formed preferable catalytic action in subsequent carbonisation.
As a preferred embodiment of the above technical solution, the process conditions of cryogenic freezing described in step (1) are as follows: by the water-setting of preparation
Glue moves into the refrigerator that temperature is -40 DEG C and carries out freezing 360min, obtains the nickel salt hydrogel of ice-like；Then it is put into rapidly
To carry out freeze-drying 6 days in -50 DEG C of refrigerator, dry xerogel presoma is obtained.
As a preferred embodiment of the above technical solution, the process conditions of high-temperature calcination described in step (1) are as follows: calcining atmosphere uses
Inert gas, heating rate are 1-20 DEG C/min, and calcination temperature is 400-1000 DEG C, soaking time 15min-5h.
As a preferred embodiment of the above technical solution, in step (2): the mass concentration of the hydrofluoric acid is 1%-40%, pyrolysis
The mass ratio of product and hydrofluoric acid is 1:5-1:50, soaking time 1min-24h.
As a preferred embodiment of the above technical solution, in step (3): the mass ratio of hollow nano-graphite carbon ball and elemental sulfur is 1:
The milling time of 1-1:10, hollow nano-graphite carbon ball and elemental sulfur is 1-6h.
As a preferred embodiment of the above technical solution, in step (3): the mixture and two of hollow nano-graphite carbon ball and elemental sulfur
The mass ratio of nitric sulfid is 1:5-1:50, and the time for continuing grinding is 1-5h.
As a preferred embodiment of the above technical solution, in step (3): the closed container is glass closed container or metal enclosed
Container, drying temperature are 150-160 DEG C, soaking time 0.5-24h.
By the ratio of hollow nano-graphite carbon ball compounding simple-substance sulfur materials and acetylene black and Kynoar 8:1:1 in mass ratio
After example mixed grinding 1-5h is until be mixed thoroughly, the slurry of black even is obtained after N-Methyl pyrrolidone is added, then apply
On cloth to aluminium foil, then drying obtains lithium sulfur battery anode material under the conditions of 60 DEG C.
Further, the calcination temperature during high temperature cabonization is because of nickel ion in the process at 400-1000 DEG C
Catalytic action could be carried out well, is lower than 400 DEG C, and carburizing temperature is inadequate, can be carbonized excessively again higher than 1000 DEG C, and also not
Conducive to reducing cost.
Further, the hydroscopic high-molecular resin is the superabsorbent particle water Sodium Polyacrylate inside diaper.
The present invention absorbs water macromolecule resin using in the products such as diaper as raw material, after absorbing nickel acetate aqueous solution,
Nickel ion is uniformly dispersed under the action of chelating effect, the catalytic growth graphitic carbon the subsequent high temperature pyrolysis under the conditions of
Ball.Hollow nano-graphite carbon ball is obtained after finally being washed off metallic nickel with hydrofluoric acid to be used to store up sulphur.This material is used for lithium
The positive electrode very good solution of sulphur battery " the shuttle effect " of lithium-sulfur cell, to improve the cycle performance of battery, simultaneously
And since graphitic carbon possesses good electron-transport dynamics, to improve the high rate performance of battery.
Compared with prior art, the invention has the following advantages:
1) the nano-graphite cavity of hollow structure provides storage sulphur space well, improves the poorly conductive of elemental sulfur
Problem；
2) many diameters be distributed in the carbon shell of hollow nano-graphite carbon ball in the micropore of 0.8nm, the presence of these micropores
Be conducive to the infiltration of elemental sulfur, while the polysulfide in battery charge and discharge process can be prevented to shuttle, to improve battery
Cycle performance (under the charging or discharging current density of 1C, circulation 1000 circle after, specific capacity can also be maintained at 658mAhg-1)；
3) advantage of graphitic carbon is exactly to have good electronics and ion transportation, and this advantage can greatly promote
The kinetics of material, to improve the high rate performance of battery, (under the conditions of the super large multiplying power of 10C, specific capacity is still maintained
450mAh·g-1)。
Detailed description of the invention
Fig. 1 is the stereoscan photograph of hollow nano-graphite carbon ball obtained by embodiment 1；
Fig. 2 is the transmission electron microscope photo of hollow nano-graphite carbon ball obtained by embodiment 1；
Fig. 3 is the transmission electron microscope photo of hollow nano-graphite carbon ball compounding simple-substance sulfur materials obtained by embodiment 1；
Fig. 4 is the XRD spectrum of hollow nano-graphite carbon ball obtained by embodiment 1；
Fig. 5 is the XRD spectrum of hollow nano-graphite carbon ball compounding simple-substance sulfur materials obtained by embodiment 1；
Fig. 6 is what hollow nano-graphite carbon ball compounding simple-substance sulfur materials obtained by embodiment 1 were prepared as positive electrode
The cycle performance figure of lithium-sulfur cell；
Fig. 7 is what hollow nano-graphite carbon ball compounding simple-substance sulfur materials obtained by embodiment 1 were prepared as positive electrode
The high rate performance figure of lithium-sulfur cell.
Specific embodiment
The present invention quotes hydrogel and constructs three-dimensional network frame structure, and wherein water-absorbing resin is as a kind of new function high score
Sub- material can lock more hydrones and aqueous solution.And hydrogel internal crosslinking braiding structure is formed, pass through metal
Graphite carbon ball is grown by metal ion catalysis during high temperature pyrolysis after gel brine freeze-drying, then by metal with harsh
After erosion, hollow nano-graphite carbon ball is obtained, obtains lithium sulfur battery anode material after most rear bearing sulphur.The material solves lithium sulphur electricity
Intrinsic problem in pond, having obtained long circulating performance, (specific capacity is still up to 658mAhg after 1000 circle of circulation-1), high power it is forthright
(under the super large multiplying power of 10C, specific capacity is still up to 450mAhg to the lithium-sulfur cell of energy-1), there is good business in energy storage field
Promotion prospect.
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
Obtained hollow nano-graphite carbon ball compounding simple-substance sulfur materials are as positive electrode system in the embodiment of the present invention
The chemical property of standby lithium-sulfur cell is tested by electrochemical workstation and blue electrical measurement test system.Electrochemical operation used
Standing is occasion China electrochemical workstation, and blue electrical measurement test system uses LAND-CT2001.Electrochemical property test uses 2032 type buttons
Battery testing, button cell assemble in the glove box full of argon gas, and the content value of water and the content value of oxygen are all protected in glove box
It holds in 0.1ppm or less.
Embodiment 1
It is a kind of that absorbent polymer resin is used to catalyze and synthesize hollow nano-graphite carbon ball compounding simple-substance for polymer template
Preparation method of the sulfur materials as lithium sulfur battery anode material.Specifically includes the following steps:
(1) hydroscopic high-molecular resin particle is collected, 1g is weighed, nickel acetate crystal 0.5g is weighed, is dissolved in 20ml distilled water
In, it is subsequently poured into absorbent polymer particle, is uniformly mixed, shake 12h using shaking table.
(2) macromolecule forms hydrogel, hydrogel is then transferred to refrigerator when nickel acetate aqueous solution is added
In -40 DEG C be tentatively frozen into ice gels freezing 6h, (removed original water-soluble finally by freeze-drying machine drying sublimation solid ice
Solvent in liquid), obtain dry Gel Precursor particle.
(3) granular precursor being transferred in tube furnace, high-temperature calcination, calcination parameter is provided that 25 DEG C of initial temperature,
3 DEG C/min of heating rate is warming up to 800 DEG C, keeps the temperature 1h, and then natural cooling cools down, and inert gas is nitrogen.
(4) precalcined product is taken out and is ground under dry environment, pickling is dry, milling time 30min, pickling
Using 20% hydrofluoric acid, 12h is stirred until etching is complete.Finally with deionized water by product centrifuge washing at neutrality, then 60
DEG C drying obtains hollow nano graphite carbon ball material.
(5) ratio of hollow nano graphite carbon ball material and simple substance sulphur powder 1:3 in mass ratio that drying obtains is mixed and is ground
Grind 1h, then be added 30mL carbon disulfide, be further continued for grinding until carbon disulfide evaporation completely, obtain uniformly mixed production
Object, then collected with closed weighing bottle, it is finally putting into 156 DEG C of heat preservation 10h of baking oven.It is compound to finally obtain hollow nano-graphite carbon ball
The sample of simple substance sulfur materials.
(6) after obtaining sample, it is made into the slurry containing conductive agent, bonding agent and organic solvent.Conductive agent
For acetylene black, bonding agent is Kynoar PVDF, and organic solvent is N-Methyl pyrrolidone NMP, is then coated on slurry
In copper foil current collector, battery is then assembled into glove box.Finally by assembled battery in blue electrical measurement test system and electrification
Work station is learned to carry out electro-chemical test and sample is carried out otherwise physical characterization etc..
The stereoscan photograph for the hollow nano-graphite carbon ball that Fig. 1 is, can be clearly seen that nano-graphite carbon ball
External morphology.
Fig. 2 is to obtain the transmission electron microscope photo of hollow nano-graphite carbon ball, can be clearly seen that hollow nano graphite carbon
The hollow structure of ball.
Fig. 3 is the transmission electron microscope photo of the hollow nano-graphite carbon ball compounding simple-substance sulfur materials finally obtained, it can be seen that
Elemental sulfur is closed in hollow carbon balls, and high-resolution lattice fringe shows (222) crystal face of sulphur, it was demonstrated that elemental sulfur
In the presence of.
Fig. 4 is the XRD spectrum of hollow nano-graphite carbon ball, and characterize graphite carbon ball is a kind of pure carbon material, and
It has been be graphitized that, belong to graphitic carbon.
Fig. 5 is the XRD spectrum of the hollow nano-graphite carbon ball compounding simple-substance sulfur materials finally obtained, characterizes hollow nanometer
Also there is the peak of graphitic carbon at the peak of the existing elemental sulfur of graphite carbon ball compounding simple-substance sulfur materials simultaneously, and the Material cladding illustrated is equal
It is even.
Fig. 6 is that the hollow nano-graphite carbon ball compounding simple-substance sulfur materials finally obtained are assembled as lithium sulfur battery anode material
Overlength cycle performance figure after lithium-sulfur cell, data show that battery after charge and discharge cycles 1000 times, still maintains in figure
658mAh·g-1Specific capacity.
Fig. 7 is that the hollow nano-graphite carbon ball compounding simple-substance sulfur materials finally obtained are assembled as lithium sulfur battery anode material
High rate capability figure after lithium-sulfur cell, data show battery under the conditions of the high current of 5C in figure, and there are also 610mAhg-1's
Specific capacity further shows that battery under the conditions of the super-large current of 10C, still there is 450mAhg-1Specific capacity.
Embodiment 2
It is a kind of that absorbent polymer resin is used to catalyze and synthesize hollow nano-graphite carbon ball compounding simple-substance for polymer template
Sulphur makees the preparation method of lithium sulfur battery anode material.Specifically includes the following steps:
(1) hydroscopic high-molecular resin particle is collected, 2g is weighed, nickel acetate crystal 1g is weighed, is dissolved in 30ml distilled water,
It is subsequently poured into absorbent polymer particle, is uniformly mixed, shake 20h using shaking table.
(2) macromolecule forms hydrogel, hydrogel is then transferred to refrigerator when nickel acetate aqueous solution is added
In -40 DEG C be tentatively frozen into ice gels freezing 6h, (removed original water-soluble finally by freeze-drying machine drying sublimation solid ice
Solvent in liquid), obtain dry Gel Precursor particle.
(3) granular precursor being transferred in tube furnace, high-temperature calcination, calcination parameter setting is as follows, and 25 DEG C of initial temperature,
2 DEG C/min of heating rate is warming up to 850 DEG C, keeps the temperature 2h, and then natural cooling cools down, and inert gas is nitrogen.
(4) precalcined product is taken out and is ground under dry environment, pickling is dry, milling time 30min, pickling
Selecting concentration is 20% hydrofluoric acid, and stirring 12h is until etching is complete.Finally with deionized water by product centrifuge washing in
Property, then 60 DEG C of drying obtain hollow nano graphite carbon ball material.
(5) ratio of hollow nano graphite carbon ball material and simple substance sulphur powder 1:3 in mass ratio that drying obtains is mixed and is ground
1h is ground, the carbon disulfide of 30mL is then added, is further continued for grinding until carbon disulfide evaporation obtains uniformly mixed product completely,
It is collected again in closed weighing bottle, is finally putting into 155 DEG C of heat preservation 6h of baking oven.Finally obtain/hollow nano-graphite carbon ball is compound
The sample of simple substance sulfur materials.
(6) after obtaining sample, it is made into the slurry containing conductive agent, bonding agent and organic solvent.Conductive agent
For acetylene black, bonding agent is Kynoar PVDF, and organic solvent is N-Methyl pyrrolidone NMP, is then coated on slurry
In copper foil current collector, battery is then assembled into glove box.Finally by assembled battery in blue electrical measurement test system and electrification
Work station is learned to carry out electro-chemical test and sample is carried out otherwise physical characterization etc..
Embodiment 3
It is a kind of that absorbent polymer resin is used to catalyze and synthesize hollow nano-graphite carbon ball compounding simple-substance for polymer template
Sulphur makees the preparation method of lithium sulfur battery anode material.Specifically includes the following steps:
(1) hydroscopic high-molecular resin particle is collected, 3g is weighed, nickel acetate crystal 2g is weighed, is dissolved in 20ml distilled water,
It is subsequently poured into absorbent polymer particle, is uniformly mixed, shake 12h using shaking table.
(2) macromolecule forms hydrogel, hydrogel is then transferred to refrigerator when nickel acetate aqueous solution is added
In -40 DEG C be tentatively frozen into ice gels freezing 6h, (removed original water-soluble finally by freeze-drying machine drying sublimation solid ice
Solvent in liquid), obtain dry Gel Precursor particle.
(3) granular precursor being transferred in tube furnace, high-temperature calcination, calcination parameter setting is as follows, and 25 DEG C of initial temperature,
1 DEG C/min of heating rate is warming up to 900 DEG C, keeps the temperature 3h, and then natural cooling cools down, and inert gas is nitrogen.
(4) precalcined product is taken out and is ground under dry environment, pickling is dry, milling time 30min, pickling
Selecting concentration is 20% hydrofluoric acid, and stirring 12h is until etching is complete.Finally with deionized water by product centrifuge washing in
Property, then 60 DEG C of drying obtain hollow nano graphite carbon ball material.
(5) ratio of hollow nano graphite carbon ball material and simple substance sulphur powder 1:3 in mass ratio that drying obtains is mixed and is ground
1h is ground, the carbon disulfide of 30mL is then added, is further continued for grinding until carbon disulfide evaporation obtains uniformly mixed product completely,
It is collected again in closed weighing bottle, is finally putting into 156 DEG C of heat preservation 10h of baking oven.Finally obtain sulphur/hollow nano-graphite carbon ball just
The sample of pole material.
(6) after obtaining sample, it is made into the slurry containing conductive agent, bonding agent and organic solvent.Conductive agent
For acetylene black, bonding agent is Kynoar PVDF, and organic solvent is N-Methyl pyrrolidone NMP, is then coated on slurry
In copper foil current collector, battery is then assembled into glove box.Finally by assembled battery in blue electrical measurement test system and electrification
Work station is learned to carry out electro-chemical test and sample is carried out otherwise physical characterization etc..
Embodiment 4
It is a kind of that absorbent polymer resin is used to catalyze and synthesize hollow nano-graphite carbon ball compounding simple-substance for polymer template
Sulfur materials make the preparation method of lithium sulfur battery anode material.Specifically includes the following steps:
(1) hydroscopic high-molecular resin particle is collected, 1000g is weighed, nickel acetate crystal 1g is weighed, is dissolved in 20ml distilled water
In, it is subsequently poured into absorbent polymer particle, is uniformly mixed, shake 12h using shaking table.
(2) macromolecule forms hydrogel, hydrogel is then transferred to refrigerator when nickel acetate aqueous solution is added
In -40 DEG C be tentatively frozen into ice gels freezing 6h, (removed original water-soluble finally by freeze-drying machine drying sublimation solid ice
Solvent in liquid), obtain dry Gel Precursor particle.
(3) granular precursor being transferred in tube furnace, high-temperature calcination, calcination parameter is provided that 25 DEG C of initial temperature,
20 DEG C/min of heating rate is warming up to 1000 DEG C, keeps the temperature 15min, and then natural cooling cools down, and inert gas is nitrogen.
(4) precalcined product is taken out and is ground under dry environment, pickling is dry, milling time 30min, pickling
Using 40% hydrofluoric acid, stirring is for 24 hours until etching is complete.Finally with deionized water by product centrifuge washing at neutrality, then 60
DEG C drying obtains hollow nano graphite carbon ball material.
(5) ratio of hollow nano graphite carbon ball material and simple substance sulphur powder 1:1 in mass ratio that drying obtains is mixed and is ground
Grind 3h, then be added 30mL carbon disulfide, be further continued for grinding until carbon disulfide evaporation completely, obtain uniformly mixed production
Object, then collected with closed weighing bottle, it is finally putting into 150 DEG C of baking oven heat preservations for 24 hours.It is compound to finally obtain hollow nano-graphite carbon ball
The sample of simple substance sulfur materials.
(6) after obtaining sample, it is made into the slurry containing conductive agent, bonding agent and organic solvent.Conductive agent
For acetylene black, bonding agent is Kynoar PVDF, and organic solvent is N-Methyl pyrrolidone NMP, is then coated on slurry
In copper foil current collector, battery is then assembled into glove box.Finally by assembled battery in blue electrical measurement test system and electrification
Work station is learned to carry out electro-chemical test and sample is carried out otherwise physical characterization etc..
Embodiment 5
It is a kind of that absorbent polymer resin is used to catalyze and synthesize hollow nano-graphite carbon ball compounding simple-substance for polymer template
Sulfur materials make the preparation method of lithium sulfur battery anode material.Specifically includes the following steps:
(1) hydroscopic high-molecular resin particle is collected, 0.01g is weighed, weighs nickel acetate crystal 10g, is dissolved in 20ml distillation
It in water, is subsequently poured into absorbent polymer particle, is uniformly mixed, shake 12h using shaking table.
(2) macromolecule forms hydrogel, hydrogel is then transferred to refrigerator when nickel acetate aqueous solution is added
In -40 DEG C be tentatively frozen into ice gels freezing 6h, (removed original water-soluble finally by freeze-drying machine drying sublimation solid ice
Solvent in liquid), obtain dry Gel Precursor particle.
(3) granular precursor being transferred in tube furnace, high-temperature calcination, calcination parameter is provided that 25 DEG C of initial temperature,
3 DEG C/min of heating rate is warming up to 400 DEG C, keeps the temperature 5h, and then natural cooling cools down, and inert gas is nitrogen.
(4) precalcined product is taken out and is ground under dry environment, pickling is dry, milling time 30min, pickling
Using 1% hydrofluoric acid, 1min is stirred until etching is complete.Finally with deionized water by product centrifuge washing at neutrality, then 60
DEG C drying obtains hollow nano graphite carbon ball material.
(5) ratio of hollow nano graphite carbon ball material and simple substance sulphur powder 1:10 in mass ratio that drying obtains is mixed and is ground
Grind 6h, then be added 30mL carbon disulfide, be further continued for grinding until carbon disulfide evaporation completely, obtain uniformly mixed production
Object, then collected with closed weighing bottle, it is finally putting into 160 DEG C of heat preservation 0.5h of baking oven.It is multiple to finally obtain hollow nano-graphite carbon ball
Close the sample of simple substance sulfur materials.
(6) after obtaining sample, it is made into the slurry containing conductive agent, bonding agent and organic solvent.Conductive agent
For acetylene black, bonding agent is Kynoar PVDF, and organic solvent is N-Methyl pyrrolidone NMP, is then coated on slurry
In copper foil current collector, battery is then assembled into glove box.Finally by assembled battery in blue electrical measurement test system and electrification
Work station is learned to carry out electro-chemical test and sample is carried out otherwise physical characterization etc..
The above description of the embodiments is intended to facilitate ordinary skill in the art to understand and use the invention.
Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein general
Principle is applied in other embodiments without having to go through creative labor.Therefore, the present invention is not limited to the above embodiments, ability
Field technique personnel announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be of the invention
Within protection scope.
Claims (10)
1. a kind of lithium sulfur battery anode material of long circulating high rate capability, which is characterized in that due to hollow nano-graphite carbon ball
And melting is loaded into the elemental sulfur composition in the hollow nano-graphite carbon ball.
2. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability as described in claim 1, special
Sign is, comprising the following steps:
(1) nickel salt solution is taken to be added in water suction macromolecule resin, uniformly mixed oscillation obtains hydrogel, and obtained hydrogel is low
After temperature freezing, drying, xerogel presoma is obtained, then by after the progress high-temperature calcination of xerogel presoma, cooling obtains pyrolysis and produces
Object；
(2) after the thermal decomposition product that step (1) obtains being mixed immersion with hydrofluoric acid, washing to neutrality, drying obtains hollow nanometer
Graphite carbon ball；
(3) the hollow nano-graphite carbon ball for obtaining step (2) and elemental sulfur mixed grinding, add carbon disulfide and continue to grind
Afterwards, drying obtains hollow nano-graphite carbon ball compounding simple-substance sulfur materials in closed container.
3. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (1): the nickel salt is nickel acetate, and the superabsorbent water macromolecule resin is Sodium Polyacrylate, nickel salt and super
The mass ratio of water suction macromolecule resin is 1:1-1:100.
4. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (1), the mixed process of nickel salt solution and water suction macromolecule resin is that constant temperature is handled in 10-50 DEG C
30min-24h。
5. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, the process conditions of cryogenic freezing described in step (1) are as follows: the hydrogel of preparation is moved into the ice that temperature is -40 DEG C
Freezing 360min is carried out in case, obtains the nickel salt hydrogel of ice-like；Then it is put into rapidly in the refrigerator for -50 DEG C carry out it is cold
Freeze 6 days, obtains dry xerogel presoma.
6. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, the process conditions of high-temperature calcination described in step (1) are as follows: calcining atmosphere uses inert gas, heating rate 1-
20 DEG C/min, calcination temperature is 400-1000 DEG C, soaking time 15min-5h.
7. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (2): the mass concentration of the hydrofluoric acid is 1%-40%, and the mass ratio of thermal decomposition product and hydrofluoric acid is
1:5-1:50, soaking time 1min-24h.
8. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (3): the mass ratio of hollow nano-graphite carbon ball and elemental sulfur is 1:1-1:10, hollow nano graphite carbon
The milling time of ball and elemental sulfur is 1-6h.
9. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (3): the mass ratio of the mixture and carbon disulfide of hollow nano-graphite carbon ball and elemental sulfur is 1:5-1:
50, the time for continuing grinding is 1-5h.
10. a kind of preparation method of the lithium sulfur battery anode material of long circulating high rate capability according to claim 2,
It is characterized in that, in step (3): the closed container is glass closed container or metal enclosed container, drying temperature 150-160
DEG C, soaking time 0.5-24h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112421044A (en) * | 2020-11-20 | 2021-02-26 | 北京理工大学重庆创新中心 | Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery |
| CN112479176A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | 3D carbon foam material, preparation method and application thereof |
| CN113224281A (en) * | 2021-03-12 | 2021-08-06 | 上海电力大学 | Lithium-sulfur battery positive electrode material taking waste diaper as raw material and preparation method |
| CN113471421A (en) * | 2021-07-23 | 2021-10-01 | 山东理工大学 | Preparation method of composite positive electrode material of lithium-sulfur battery |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN103828101A (en) * | 2011-05-31 | 2014-05-28 | 汉阳大学校产学协力团 | Method for manufacturing carbon-sulfur composite, carbon-sulfur composite manufactured thereby, and lithium-sulfur battery including same |
| CN104577080A (en) * | 2014-12-29 | 2015-04-29 | 中国地质大学（武汉） | Composite cathode material used for lithium-sulfur battery and having high-rate performance and preparation method |
| US20160233492A1 (en) * | 2013-09-30 | 2016-08-11 | Robert Bosch Gmbh | Sulfur-containing composite for lithium-sulfur battery, a process for preparing said composite, and the electrode material and lithium-sulfur battery comprising said composite |
| CN106920950A (en) * | 2017-04-25 | 2017-07-04 | 上海电力学院 | A kind of preparation method of high circulation, powerful carbon based negative electrodes energy-storage composite material |
| CN107768643A (en) * | 2017-10-19 | 2018-03-06 | 山东大学 | A kind of carbon ball/sulphur/redox graphene composite for lithium-sulfur cell and preparation method thereof |
| CN108448101A (en) * | 2018-04-12 | 2018-08-24 | 深圳大学 | Lithium sulfur battery anode material and its preparation method and application |
-
2018
- 2018-08-27 CN CN201810982290.2A patent/CN109244393B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177269A (en) * | 2007-12-13 | 2008-05-14 | 复旦大学 | Meso-porous structural high specific surface carborundum material and preparation method thereof |
| CN103828101A (en) * | 2011-05-31 | 2014-05-28 | 汉阳大学校产学协力团 | Method for manufacturing carbon-sulfur composite, carbon-sulfur composite manufactured thereby, and lithium-sulfur battery including same |
| US20160233492A1 (en) * | 2013-09-30 | 2016-08-11 | Robert Bosch Gmbh | Sulfur-containing composite for lithium-sulfur battery, a process for preparing said composite, and the electrode material and lithium-sulfur battery comprising said composite |
| CN104577080A (en) * | 2014-12-29 | 2015-04-29 | 中国地质大学（武汉） | Composite cathode material used for lithium-sulfur battery and having high-rate performance and preparation method |
| CN106920950A (en) * | 2017-04-25 | 2017-07-04 | 上海电力学院 | A kind of preparation method of high circulation, powerful carbon based negative electrodes energy-storage composite material |
| CN107768643A (en) * | 2017-10-19 | 2018-03-06 | 山东大学 | A kind of carbon ball/sulphur/redox graphene composite for lithium-sulfur cell and preparation method thereof |
| CN108448101A (en) * | 2018-04-12 | 2018-08-24 | 深圳大学 | Lithium sulfur battery anode material and its preparation method and application |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112479176A (en) * | 2020-10-26 | 2021-03-12 | 温州大学 | 3D carbon foam material, preparation method and application thereof |
| CN112421044A (en) * | 2020-11-20 | 2021-02-26 | 北京理工大学重庆创新中心 | Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery |
| CN112421044B (en) * | 2020-11-20 | 2021-12-10 | 北京理工大学重庆创新中心 | Core-shell structure sulfur positive electrode material, preparation method and application in lithium-sulfur battery |
| CN113224281A (en) * | 2021-03-12 | 2021-08-06 | 上海电力大学 | Lithium-sulfur battery positive electrode material taking waste diaper as raw material and preparation method |
| CN113471421A (en) * | 2021-07-23 | 2021-10-01 | 山东理工大学 | Preparation method of composite positive electrode material of lithium-sulfur battery |
| CN113471421B (en) * | 2021-07-23 | 2022-03-29 | 山东理工大学 | Preparation method of composite positive electrode material of lithium-sulfur battery |
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