CN110148723A - A kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material - Google Patents
A kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material Download PDFInfo
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- CN110148723A CN110148723A CN201910415733.4A CN201910415733A CN110148723A CN 110148723 A CN110148723 A CN 110148723A CN 201910415733 A CN201910415733 A CN 201910415733A CN 110148723 A CN110148723 A CN 110148723A
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Abstract
The present invention discloses a kind of SnS with high performance2The preparation method and application of@nitrogen-doped carbon compound kalium ion battery negative electrode material;The collagen protein powder extracted in the discarded ox-hide hair of the slave leather industry is waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source coating modification SnS2Graduation microballoon, can effectively improve the storage potassium performance of material.Technical solution is as follows: extracting from discarded ox hair and obtains collagen protein powder, tin source, sulphur source and collagen protein powder are successively added to ultrasound, magnetic agitation in dehydrated alcohol;Mixed solution is put into microwave reaction case and is reacted, 5%H is led in centrifuge washing drying2The calcining of/95%Ar gaseous mixture, which is made, has good storage potassium characteristic SnS2@nitrogen-doped carbon compound.The preparation process is simple, waste high-qualityization utilize, strong operability, raw material sources extensively and resources circulation, it is low in cost, can be mass-produced, meet environmental requirement.
Description
Technical field
The invention belongs to kalium ion battery Material Field more particularly to a kind of SnS with high performance2@nitrogen-doped carbon is multiple
Close the preparation method and application of object.
Background technique
In secondary energy sources storage system, lithium ion battery is received significant attention, and high speed development, we live in
Locate visible (portable electronic products, communication apparatus, electric car etc.).However consider the finiteness of metal lithium resource, a large amount of lithiums
Consumption made lithium resource increasingly deficient, only solely rely on lithium ion battery and be unable to satisfy the mankind to following need
It asks.And have the metallic potassium of the same clan of similar physics and chemical property with lithium, reserves more horn of plenty, and energy storage mechnism is similar, because
This kalium ion battery is most to be expected to replace one of the battery of lithium ion battery applications in we live.
However because potassium ion has the atomic radius bigger than lithium ion, existing major part lithium ion battery is negative
The all unsuitable storage potassium of pole material, is primarily due to the problems such as interlamellar spacing is small, and dynamics is slow.Therefore finding has specific capacity
It is high, can stable/embedding potassium electrode material have great importance.And artificial gold has special layer structure, has very high
Storage potassium theoretical capacity (733 mAh g-1) and preferable storage potassium characteristic.However, artificial gold volume expansion when storing up potassium is huge, and
Electric conductivity is poor, and conventional method of modifying is complex carbon material to improve its electric conductivity, and part inhibits its huge volume swollen
It is swollen.The invention patent is using the collagen protein powder of discarded ox-hide hair preparation as structure inducer, nano-reactor and N doping
Carbon source, to construct SnS2@nitrogen-doped carbon graduation microballoon, this can not only effectively slow down volume expansion bring material dusting, knot
The problems such as structure collapses, and nitrogen atom doping can make the more active sites of material exposure, to improve the storage potassium performance of material.
The present invention by using discard the preparation of ox-hide hair collagen as structure inducer, nano-reactor and N doping
Carbon source prepares SnS2@nitrogen-doped carbon compound.It is compared difference with conventional method and is: 1, N doping carbon source is from process hides
The collagen that the discarded ox-hide hair of industry extracts, it is from a wealth of sources, and turn waste into wealth, more meet resources circulation as raw material
With the strategy of Green Development;2, nitrogen-doped carbon can not only improve the structural stability and electric conductivity of material as substrate, moreover it is possible to sudden and violent
Reveal more active sites, optimizes the storage potassium performance of material;3, collagen is fine by the collagen of chain as structure inducer
Dimension complexing confinement tin source and sulphur source, induce SnS2It is grown to the graduation micro-sphere structure of two-dimensional ultrathin piece composition;4, pass through microwave
Solvent-thermal method constructs SnS2@nitrogen-doped carbon composite material, method is simple, and preparation quickly, has the prospect of large-scale production;5,
SnS2@nitrogen-doped carbon compound has special graduation micro-sphere structure, can effectively inhibit electrode material during storing up potassium
Volume expansion;And the result shows that, which has excellent storage potassium performance, has application prospect.
Summary of the invention
The purpose of the present invention is to provide a kind of SnS with high performance2@nitrogen-doped carbon compound and preparation method thereof and
Using, simple process, strong operability, the discarded ox-hide hair of raw material sources leather industry, waste higher value application is at low cost
It is honest and clean, it can be mass-produced, meet environmental requirement.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of SnS with high performance2The preparation method of@nitrogen-doped carbon compound kalium ion battery negative electrode material, including it is as follows
Step:
1) first discarded ox-hide hair is washed with deionized water, then 50-80 °C at a temperature of dry, then ground
At fur powder;And be placed on fur powder in 30-50 °C of solder(ing)acid water-bath 1-2 hours, it is filtered, washed to neutrality, so
It is dried at a temperature of 50-70 °C afterwards;Finally powder is added in ionic liquid, 90-120 °C at a temperature of stir strongly
1-3 hours, freeze-drying obtained collagen protein powder;
2) tin source, sulphur source and collagen protein powder for weighing certain mass are added in dehydrated alcohol, and elder generation is ultrasonic after a certain period of time, then
Magnetic agitation 20-40 minutes;Mixed solution is put into 150-200 °C of microwave reaction case, and solvent heat 0.5-1 hours, centrifugation was washed
It washs, black gray expandable powder is collected in 80 °C of drying;
3) black gray expandable powder obtained by step 2 is put into quartz boat, is 5%H in volume ratio2In/95%Ar atmosphere tube type furnace
350-650 °C calcining 2-4 hours, collect black solid sample, as SnS2@nitrogen-doped carbon compound.
Above-mentioned steps 1) in, the collagen protein powder is made using the discarded ox-hide hair of leather industry as raw material, work
Skill is easy, is a kind of waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source coating modification
SnS2Graduation microballoon;The ionic liquid is choline chloride and quality of glycol than the mixed solution for 1:2;The tin
Source is that series contains pink salt, including is not limited to stannous chloride, stannic chloride, stannous sulfate;Tin source and collagen protein powder mass ratio
For 1:0.5-1;In step 2, the tin source: sulphur source: the mass ratio of collagen protein powder is 4-8: 4-10: 3-5, collagen egg
White powder: the mass volume ratio of dehydrated alcohol is 3-5 g:0.3-1 L.
SnS with high performance made from the above-mentioned preparation method of the present invention2@nitrogen-doped carbon compound kalium ion battery is negative
Pole material is SnS2@nitrogen-doped carbon compound.
The SnS with high performance2@nitrogen-doped carbon compound kalium ion battery negative electrode material, it is characterised in that:
SnS2@nitrogen-doped carbon compound has graduation micro-sphere structure;The collagen protein powder is waste higher value application product,
And there is nitrogen-atoms abundant, can effectively improve the chemical property of material.
SnS with high performance made from the above-mentioned preparation method of the present invention2@nitrogen-doped carbon compound kalium ion battery is negative
Pole material is SnS2The application of@nitrogen-doped carbon compound, it is characterised in that: the SnS2@nitrogen-doped carbon compound is applied to potassium
In ion battery cathode, when voltage is 0.01-3.0 V, 1 A/g of high current density after charge and discharge cycles 100 times, specific capacity is steady
240 mAh/g or more are scheduled on, capacity retention ratio is up to 90% or more.
A kind of kalium ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: claim 1-2
SnS with high performance made from any preparation method2@nitrogen-doped carbon compound kalium ion battery negative electrode material: it leads
The electric super P carbon of agent: it is equably coated in after binder CMC=80:10:10 mixed grinding on copper foil as working electrode, metallic potassium
Piece is to electrode, the KPF of 1 mol/L6/ EC (ethylene carbonate), PC(propene carbonate) it is that electrolyte is assembled into 2025 types
Button-type battery;All assemblings carry out in inert-atmosphere glove box.
Remarkable advantage of the invention is:
1) present invention used in collagen protein powder from leather industry discarded ox-hide hair, it is from a wealth of sources, belong to process hides work
The waste higher value application of industry.Functioning as presoma nitrogen source, being doped in carbon material for collagen protein powder, can make material
The more active sites of exposure, improve the storage potassium performance of material, to obtain SnS2@nitrogen-doped carbon compound.
2) nitrogen-doped carbon used in the present invention functions as carrier, plays to the artificial gold graduation microballoon auxiliary
The electric conductivity of the buffer function, increase material that help and the infiltration for being conducive to electrolyte.On the one hand, nitrogen-doped carbon and artificial gold is slow
It rushes system and provides certain free space for the volume expansion and contraction of artificial gold during de-/embedding potassium.On the other hand, nitrogen is mixed
Miscellaneous carbon is conducive to the diffusion of electrolyte, electron conductivity is helped to improve, and can effectively fix artificial gold structure, into one
Step improves it and stores up potassium performance.
3) present invention synthesizes SnS dexterously using the collagen of discarded ox-hide hair preparation as N doping carbon source2@nitrogen
Adulterate carbon complex, the SnS that the embodiment of the present invention 1 obtains2@nitrogen-doped carbon compound is applied in kalium ion battery cathode,
Voltage be 0.01-3.0 V, 1 A/g of high current density when charge and discharge cycles 100 times after, specific capacity stablize 240 mAh/g with
On, capacity retention ratio is up to 90% or more.
4) SnS2@nitrogen-doped carbon compound is a kind of good kalium ion battery negative electrode material, and the present invention provides one kind
Prepare SnS2The method of@nitrogen-doped carbon compound, the preparation process is simple, and equipment is easy to get, strong operability, and leather industry is given up
Gurry higher value application, raw material sources are extensive and environmentally protective, low in cost, can mass production, meet environmental requirement.
Detailed description of the invention
Fig. 1 is the resulting SnS of embodiment 12The XRD diagram of@nitrogen-doped carbon compound.
Fig. 2 is the resulting SnS of embodiment 12The SEM of@nitrogen-doped carbon compound schemes.
Fig. 3 is the resulting SnS of embodiment 12In 50 mA/ when@nitrogen-doped carbon compound is as kalium ion battery negative electrode material
Charging and discharging curve figure under g current density.
Fig. 4 is the resulting SnS of embodiment 12In 1 A/g when@nitrogen-doped carbon compound is as kalium ion battery negative electrode material
Long-life cycle performance figure under current density.
Specific embodiment
Embodiment 1
1) first discarded ox-hide hair (the discarded ox-hide for referring to hairiness) is washed with deionized water, then at a temperature of 50 °C
Drying, then it is milled to fur powder;And be placed on fur powder in 30 °C of solder(ing)acids water-bath 2 hours, it filters, wash
It washs to neutrality, is then dried at a temperature of 50 °C;Powder is finally added to choline chloride and quality of glycol than for 1:2's
In ionic liquid, 90 °C at a temperature of stir strongly 3 hours, freeze-drying obtain collagen protein powder;
2) 4 g stannous chlorides are weighed respectively, 6 g L-cysteines and 4 g collagen protein powders are added in 0.6 L dehydrated alcohol,
First ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 150 °C of microwave reaction casees, and solvent heat 0.6 hour,
Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, is 5%H in volume ratio2350 in/95%Ar atmosphere tube type furnace
°C calcining 2 hours, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound kalium ion battery is negative
Pole material --- SnS2@nitrogen-doped carbon compound;
The SnS for obtaining Fig. 1 is tested through XRD2The XRD diagram of@nitrogen-doped carbon compound, from fig. 1, it can be seen that the material that synthesis obtains is sulphur
The standard diagram (JCPDS, 022-0951) of change tin, diffraction maximum position and artificial gold matches.It tests and obtains through scanning electron microscope
The SnS of Fig. 22The SEM of@nitrogen-doped carbon compound schemes.The compound is graduation micro-sphere structure as shown in Figure 2, and surface is by piece
The artificial gold of shape is formed;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred
Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1
The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings
It is carried out in inert-atmosphere glove box.At 100 mA/g and 1 A/g current density, it is tested respectively and stores up potassium performance.Fig. 3
It is charging and discharging curve of the material under 50 mA/g current densities, as can be seen from the figure the electrode material is discharging it for the first time
Afterwards, charging and discharging curve repeatability is preferable, illustrates it with good cyclical stability.As shown in Figure 4, SnS2@nitrogen-doped carbon is multiple
When closing object as kalium ion battery negative electrode material, excellent storage potassium performance is shown, in the case where voltage is 0.01-3.0 V, in big electricity
100 specific capacities of charge and discharge cycles are stablized in 240 mAh/g when 1 A/g of current density, and capacity is unattenuated.Therefore, SnS2@N doping
Carbon complex has good storage potassium performance, is environmentally friendly high-performance kalium ion battery negative electrode material, has good
Application prospect.
Embodiment 2
1) first discarded ox-hide hair (the discarded ox-hide for referring to hairiness) is washed with deionized water, then at a temperature of 60 °C
Drying, then it is milled to powder;And be placed on fur powder in 40 °C of solder(ing)acids water-bath 1.5 hours, it is filtered, washed
To neutrality, then dried at a temperature of 50 °C;Finally by powder be added to choline chloride and quality of glycol than for 1:2 from
In sub- liquid, 100 °C at a temperature of stir strongly 1 hour, freeze-drying obtain collagen protein powder;
2) 4 g stannic chlorides are weighed respectively, and 4 g L-cysteines and 3 g collagen protein powders are added in 0.3 L dehydrated alcohol, first
Ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 170 °C of microwave reaction casees, and solvent heat 0.5 hour, from
Heart washing, 80 °C of drying, collects black gray expandable powder;
3) it by black gray expandable powder obtained by step 1), is put into quartz boat, in 5%H2500 °C of calcinings in/95%Ar atmosphere tube type furnace
2 hours, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred
Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1
The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal
It is carried out in inert-atmosphere glove box.
Embodiment 3
1) first discarded ox-hide hair (ox-hide for referring to hairiness) is washed with deionized water, then 70 °C at a temperature of dry,
It is milled to powder again;And be placed on fur powder in 50 °C of solder(ing)acids water-bath 1 hour, it is filtered, washed to neutrality,
Then it is dried at a temperature of 60 °C;Powder is finally added to choline chloride and quality of glycol than the ionic liquid for 1:2
In, 110 °C at a temperature of stir strongly 1 hour, freeze-drying obtain collagen protein powder;
2) 6 g stannous sulfates are weighed respectively, and 9 g L-cysteines and 5 g collagen protein powders are added in 1 L dehydrated alcohol, first
Ultrasound 10 minutes, then magnetic agitation 30 minutes;Mixed solution is put into 190 °C of microwave reaction casees, and solvent heat 0.5 hour,
Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, in 5%H2500 °C of calcinings 4 in/95%Ar atmosphere tube type furnace
Hour, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred
Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1
The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal
It is carried out in inert-atmosphere glove box.
Embodiment 4
1) first discarded ox-hide hair (ox-hide for referring to hairiness) is washed with deionized water, then 80 °C at a temperature of dry,
It is milled to powder again;And be placed on fur powder in 50 °C of solder(ing)acids water-bath 1 hour, it is filtered, washed to neutrality,
Then it is dried at a temperature of 70 °C;Powder is finally added to choline chloride and quality of glycol than the ionic liquid for 1:2
In, 120 °C at a temperature of stir strongly 2 hours, freeze-drying obtain collagen protein powder;
2) 8 g stannous chlorides are weighed respectively, and 4 g L-cysteines and 5 g collagen protein powders are added in 1 L dehydrated alcohol, first
10 min of ultrasound, then 30 min of magnetic agitation;Mixed solution is put into 200 °C of microwave reaction casees, and microwave solvothermal 0.5 hour,
Centrifuge washing, 80 °C of drying, collects black gray expandable powder;
3) black gray expandable powder obtained by step 1) is put into quartz boat, in 5%H2600 °C of calcinings 4 in/95%Ar atmosphere tube type furnace
Hour, collect black solid sample, SnS as with high performance2@nitrogen-doped carbon compound;
Using SnS manufactured in the present embodiment2@nitrogen-doped carbon compound: the super P carbon of conductive agent: binder CMC is according to quality hundred
Point than being equably coated on copper foil electrode of working after 80: 10: 10 mixed grindings, metallic potassium piece is to electrode, and 1
The KPF of mol/L6/ EC, PC (ethylene carbonate, propene carbonate) are that electrolyte is assembled into button cell;All assemblings are equal
It is carried out in inert-atmosphere glove box.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (6)
1. a kind of SnS with high performance2The preparation method of@nitrogen-doped carbon compound kalium ion battery negative electrode material, including it is as follows
Step:
1) first discarded ox-hide hair is washed with deionized water, then 50-80 °C at a temperature of dry, then ground
At fur powder;And be placed on fur powder in 30-50 °C of solder(ing)acid water-bath 1-2 hours, it is filtered, washed to neutrality, so
It is dried at a temperature of 50-70 °C afterwards;Finally powder is added in ionic liquid, 90-120 °C at a temperature of stir strongly
1-3 hours, freeze-drying obtained collagen protein powder;
2) tin source, sulphur source and collagen protein powder for weighing certain mass are added in dehydrated alcohol, and elder generation is ultrasonic after a certain period of time, then
Magnetic agitation 20-40 minutes;Mixed solution is put into 150-200 °C of microwave reaction case, and solvent heat 0.5-1 hours, centrifugation was washed
It washs, black gray expandable powder is collected in 80 °C of drying;
3) black gray expandable powder obtained by step 2 is put into quartz boat, is 5%H in volume ratio2350- in/95%Ar atmosphere tube type furnace
650 °C calcining 2-4 hours, collect black solid sample, as SnS2@nitrogen-doped carbon compound.
2. SnS with high performance according to claim 12The system of@nitrogen-doped carbon compound kalium ion battery negative electrode material
Preparation Method, it is characterised in that: in step 1), the collagen protein powder is using the discarded ox-hide hair of leather industry as raw material system
, simple process is a kind of waste higher value application product, can be used as two-dimensional structure inducer and N doping carbon source cladding changes
Property SnS2Graduation microballoon;The ionic liquid is choline chloride and quality of glycol than the mixed solution for 1:2;Described
Tin source is that series contains pink salt, including is not limited to stannous chloride, stannic chloride, stannous sulfate;Tin source and collagen protein powder quality
Than for 1:0.5-1;In step 2, the tin source: sulphur source: the mass ratio of collagen protein powder is 4-8: 4-10: 3-5, collagen
Albumen powder: the mass volume ratio of dehydrated alcohol is 3-5 g:0.3-1 L.
3. SnS with high performance made from any preparation method of claim 1-22@nitrogen-doped carbon compound potassium ion
Cell negative electrode material is SnS2@nitrogen-doped carbon compound.
4. SnS with high performance according to claim 32@nitrogen-doped carbon compound kalium ion battery negative electrode material,
It is characterized in that: SnS2@nitrogen-doped carbon compound has graduation micro-sphere structure;The collagen protein powder is that waste is high-valued
Using product, and there is nitrogen-atoms abundant, can effectively improve the chemical property of material.
5. SnS with high performance made from any preparation method of claim 1-22@nitrogen-doped carbon compound potassium ion
Cell negative electrode material is SnS2The application of@nitrogen-doped carbon compound, it is characterised in that: the SnS2@nitrogen-doped carbon compound is answered
For in kalium ion battery cathode, when voltage is 0.01-3.0 V, 1 A/g of high current density after charge and discharge cycles 100 times, than
Capacity is stablized in 240 mAh/g or more, and capacity retention ratio is up to 90% or more.
6. a kind of kalium ion battery, including working electrode and to electrode, it is characterised in that: in mass ratio are as follows: claim 1-2 appoints
SnS with high performance made from preparation method described in one2@nitrogen-doped carbon compound kalium ion battery negative electrode material: conductive
The super P carbon of agent: it is equably coated in after binder CMC=80:10:10 mixed grinding on copper foil as working electrode, metallic potassium piece
For to electrode, the KPF of 1 mol/L6/ EC (ethylene carbonate), PC(propene carbonate) it is that electrolyte is assembled into 2025 type knobs
Button-type battery.
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CN112018358A (en) * | 2020-08-17 | 2020-12-01 | 五邑大学 | Nitrogen-doped/carbon-coated potassium titanate material and preparation method thereof |
CN112038596A (en) * | 2020-08-17 | 2020-12-04 | 嵊州市芝草科技有限公司 | Mesoporous carbon coated SnS2The negative electrode material of the sodium ion battery and the preparation method thereof |
CN112194173A (en) * | 2020-09-30 | 2021-01-08 | 中南大学 | Preparation method of tin sulfide/nitrogen doped flower-like carbon lithium ion battery cathode material and product thereof |
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CN112194173B (en) * | 2020-09-30 | 2021-06-22 | 中南大学 | Preparation method of tin sulfide/nitrogen doped flower-like carbon lithium ion battery cathode material and product thereof |
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