CN109167035A - Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation - Google Patents
Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation Download PDFInfo
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- CN109167035A CN109167035A CN201810961175.7A CN201810961175A CN109167035A CN 109167035 A CN109167035 A CN 109167035A CN 201810961175 A CN201810961175 A CN 201810961175A CN 109167035 A CN109167035 A CN 109167035A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to a kind of carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion batteries of preparation, carbon-coated ferrous sulfide negative electrode material refers to carbon-coated ferrous sulfide and its doping and modification material, wherein ferrous sulfide grain diameter is 100 ~ 500 nm, the quality of carbon coating layer is the 3% ~ 30% of electrode material quality, doping and modification element is one or more of M=Co, Ni, Mn, Ti, Cu, Mg, Ba, Pb, Al etc., and the quality of doping and modification element is the 0 ~ 30% of cathode quality of materials.Preparation method is that metal sulfate and carbon source are added in deionized water, and dissolution is stirred at room temperature and is freeze-dried obtained presoma after mixing, carbon-coated ferrous sulfide negative electrode material is made in high-temperature calcination under an inert atmosphere.The present invention has the advantages that simple abundant raw material, preparation, short preparation period, at low cost, pollution-free, good rate capability and cyclical stability are strong as anode material of lithium-ion battery, and is suitble to large-scale production.
Description
Technical field
The present invention relates to field of new energy technologies, and in particular to a kind of carbon-coated ferrous sulfide negative electrode material, preparation side
Method and its sodium-ion battery of preparation.
Background technique
Lithium ion battery has many advantages, such as that small in size, voltage is high, energy density is high as chemical energy source.Lithium ion battery exists
It is used widely in human lives, is answered from small devices such as mobile phone, computers to electric car, smart grid etc. are high-power
Use equipment.But lithium resource uneven distribution, it is at high cost the features such as, limit the large-scale application of lithium ion battery.Sodium ion
Battery and lithium ion battery have similar working principle, while the advantages that, rich reserves cheap with its, downwards one
For fields such as communications and transportation and power grids, there is unique advantage.
The advantages that transient metal sulfide is because of its specific capacity height, good conductivity, in anode material of lithium-ion battery field
It receives more and more attention.But the volume expansion in charge and discharge process of such material is serious, polysulfide in cyclic process
Dissolution in the electrolytic solution causes the loss of active material, causes capacity to reduce and is deteriorated with cyclical stability.Particle nanosizing and
Material with carbon-coated surface is the available strategy for solving problems, but the usual complex process of synthetic method reported at present, production
It is at high cost, and organic solvent is mostly used, it can cause environmental pollution.
To finding, a kind of specific capacity is high, stable circulation is good, abundant raw material, cheap, simple, the free of contamination cathode of synthesis
The exploration of material synthesis method is carrying out always.Kim seminar has been dissolved in 80 DEG C of deionized waters by using ferrous sulfate
Quan Hou is added glycine and does ligand, and terminator citric acid is added until after complexing completely in heating stirring, completely molten to citric acid
Solution is transferred to 110 DEG C of baking oven heated dryings and generates metal organic complex presomas by solution, and calcining generates nitrogen, sulphur codope
The carbon-coated ferrous sulfide of honeycomb is used as lithium ion battery negative material (Carbon, 2017,115:249 ~ 364).But
It is that its raw material type is more, synthesis step is relative complex, and time-consuming.
Summary of the invention
The invention proposes a kind of carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium ion of preparation electricity
Pond, the material have simple abundant raw material, preparation, short preparation period, at low cost, pollution-free, suitable the advantages of being mass produced.
Meanwhile the material has the advantages that the electrochemistry that capacity is high, good rate capability and cyclical stability are strong.In addition, what is invented includes
The sodium-ion battery of the material has a vast market application prospect as battery of new generation.
It realizes the technical scheme is that a kind of carbon-coated ferrous sulfide negative electrode material, negative electrode material is carbon coating
Ferrous sulfide material, the quality of carbon coating layer is the 3% ~ 30% of cathode quality of materials, ferrous sulfide grain diameter is 100 ~
500nm。
In the negative electrode material also contain doping and modification element, doping and modification element be Co, Ni, Mn, Ti, Cu, Mg, Ba,
One or more of Pb, Al；The quality of carbon coating layer is the 3% ~ 30% of cathode quality of materials, doping and modification member in negative electrode material
The quality of element is the 0 ~ 30% of cathode quality of materials.
The preparation method of the carbon-coated ferrous sulfide negative electrode material, steps are as follows:
(1) carbon source and ferrous sulfate or doping metals sulfate are dissolved in deionized water, -40 after being uniformly mixed ~ -
Presoma is made in 56 DEG C of 6 ~ 60h of freeze-drying；
(2) after the grinding of presoma that step (1) obtains being placed on 500 ~ 850 DEG C of calcinings 1 in the tube furnace of inert atmosphere ~ for 24 hours
Obtain carbon-coated ferrous sulfide negative electrode material.
Carbon source in the step (1), ferrous sulfate, doping metals sulfate and deionized water mass ratio be (1 ~ 10):
1:(0 ~ 1): (4 ~ 1000).
Carbon source is one or more of citric acid, ascorbic acid, glucose in the step (1)；Doping metals sulfuric acid
Salt is iron ammonium sulfate, cobaltous sulfate, nickel sulfate, manganese sulfate, titanium sulfate, copper sulphate, magnesium sulfate, barium sulfate, lead sulfate, aluminum sulfate
One or more of.
The sodium-ion battery of the carbon-coated ferrous sulfide negative electrode material preparation, including positive plate, negative electrode tab, electrolysis
Liquid, diaphragm and shell, sodium-ion battery using can embedding removing sodium active material as positive electrode, carbon-coated ferrous sulfide cathode
For material as negative electrode material, diaphragm is fibreglass diaphragm, polypropylene diaphragm, polyethylene diagrams and modified cellulose acetate membrane
One or more of, soluble sodium salt organic solution is electrolyte.
It is described can embedding removing sodium active material be Na3V2(PO4)3、Na3V2(PO4)2F3、NaFePO4、NaMnO2、NaFeO2、
FePO4、Na2.4Fe1.8(SO4)3、Na4Fe(CN)6、Na4Co3(PO4)2P2O7One of electrode material is several.
The soluble sodium salt organic solution is that sodium salt is dissolved in organic solvent and obtaining, the sodium salt be sodium hexafluoro phosphate,
The one or more of sodium perchlorate, trifluoromethyl sulfonate and bis trifluoromethyl sulfimide sodium, organic solvent are ethylene carbonates
One or more of ester, propene carbonate, diethyl carbonate, diethylene glycol dimethyl ether and triglyme.
The positive plate and negative electrode tab pass through positive electrode and negative electrode material respectively and conductive agent, binder and dispersing agent are equal
Obtained slurry full-filling is obtained to collector after even mixing, and collector is carbon cloth, metal stainless steel, nickel and aluminium it is porous,
Netted or thin-film material；The conductive agent is one or more of acetylene black, carbon black, graphite or Super P Li；Bonding
Agent is polytetrafluoroethylene (PTFE), Kynoar, sodium carboxymethylcellulose, polyacrylic acid, polyvinylidene fluoride, sodium alginate, gelatin
Or one or more of butadiene-styrene rubber；Dispersing agent be one of water, ethyl alcohol, isopropanol or 1-Methyl-2-Pyrrolidone or
It is several.
The shell use organic plastics, aluminum hull, aluminum plastic film, stainless steel and its composite material, shape be button, column or
It is rectangular.
The beneficial effects of the present invention are: the present invention only passes through two kinds of raw materials of ferrous sulfate and carbon source in room temperature in deionized water
In be uniformly mixed, uniform carbon-coated ferrous sulfide can be obtained in calcining after freeze-drying, can be successfully used as sodium-ion battery
Negative electrode material shows excellent cyclical stability and high rate performance.Such preparation method is simply easy to be mass produced simultaneously,
Have a vast market application prospect.Carbon-coated ferrous sulfide and its doping and modification substance are as in sodium-ion battery system
Negative electrode material, the short transmission path of nanostructure and carbon coating in situ can be effectively relieved material volume expansion, poorly conductive and
The problems such as polysulfide dissolves, while the electrode material cycle performance and high rate performance are excellent.The material feedstock is cheap, molten
Agent is pollution-free, and preparation method is simple to operation, time-consuming short, is suitble to large-scale production, is expected to realize commercialization.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
It obtains other drawings based on these drawings.
Fig. 1 is X ~ x ray diffraction (XRD) figure of carbon-coated ferrous sulfide prepared by embodiment 1.
Fig. 2 is scanning electron microscope (SEM) figure of carbon-coated ferrous sulfide prepared by embodiment 1.
Fig. 3 is battery first all charging and discharging curve of the carbon-coated ferrous sulfide as negative electrode material of the preparation of embodiment 1.
Fig. 4 is battery high rate performance figure of the carbon-coated ferrous sulfide of the preparation of embodiment 2 as negative electrode material.
Fig. 5 is that the sodium-ion battery head that carbon-coated ferrous sulfide prepared by embodiment 3 is assembled as negative electrode material fills in week
Discharge curve.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical solution of the present invention is clearly and completely described, it is clear that institute
The embodiment of description is only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention,
Those of ordinary skill in the art's every other embodiment obtained under that premise of not paying creative labor, belongs to this hair
The range of bright protection.
Embodiment 1
Carbon-coated ferrous sulfide agent particle size is 100 ~ 500nm in the present embodiment, and wherein the quality of clad is the material matter
The 10% of amount.
The synthesis step of carbon-coated ferrous sulfide substance used in the present invention is as follows:
(1) it weighs 0.96 g green vitriol and 2.18 g monohydrate potassiums is dissolved in 7 mL deionized waters and stirs
Presoma is made in -56 DEG C of freeze-dryings for 24 hours after mixing；
(2) the presoma grinding that step (1) obtains is placed on 800 DEG C of calcining 6h in the tube furnace of inert atmosphere, grinding system
Obtain carbon-coated ferrous sulfide substance.
Fig. 1 is X ~ x ray diffraction (XRD) figure of carbon-coated ferrous sulfide substance, the standard card with ferrous sulfide
JCPDS 37 ~ 0477 is corresponding, and crystallinity is good.Fig. 2 is carbon-coated ferrous sulfide substance scanning electron microscope
(SEM) figure, the diameter range of ferrous sulfide nano particle are 100 ~ 500nm, and wherein the quality of carbon coating layer is electrode material matter
The 10% of amount.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (Super
P Li), sodium carboxymethylcellulose with 80:10:10 mass ratio mixing, use deionized water for dispersing agent, said mixture mixed
Conjunction is uniformly tuned into slurry and is applied on copper foil, cuts out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is to electrode (negative electrode plate
Capacity is much larger than cut out positive plate capacity), cathode pole piece is separated with metallic sodium piece using Whatman glass fibre membrane,
Use 1 M NaClO4Being dissolved in EC:PC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is as shell, group
Dress up CR2025 formula button cell, the battery that the above process is assembled at room temperature, charge and discharge in the potential range of 0.01 ~ 2.5 V
Electrical testing, charging and discharging curve are as shown in Figure 4.Its charging and discharging curve is as shown in Figure 3.First week charge specific capacity is 597.5 Ma
H/g, specific discharge capacity 649.45mAh/g, coulombic efficiency 92%.
Embodiment 2
The preparation of the carbon-coated ferrous sulfide substance of the present embodiment is the same as embodiment 1.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (Super
P Li), sodium carboxymethylcellulose with 80:10:10 mass ratio mixing, use deionized water for dispersing agent, said mixture mixed
Conjunction is uniformly tuned into slurry and is applied on copper foil, cuts out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is (to hold electrode electrode
Amount is much larger than cut out negative electrode tab capacity), cathode pole piece is separated with metallic sodium piece using Whatman glass fibre membrane, is made
With 1 M NaCF3SO3Being dissolved in diethylene glycol dimethyl ether is electrolyte, and stainless steel steel shell is assembled into CR2025 formula knob as shell
Detain battery, the battery that the above process is assembled at room temperature, charge-discharge test in the potential range of 0.3 ~ 2.5 V.It is forthright again
It can be as shown in Fig. 4.In 10 A g-1Multiplying power under, specific discharge capacity can reach 315.4mAh/g, 2 A g-1Current density
Material still maintains the capacity of 374.7mAh/g, capacity retention ratio 92% after lower 800 weeks circulations.
Embodiment 3
The preparation of the carbon-coated ferrous sulfide substance of the present embodiment is the same as embodiment 1.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (Super
P Li), sodium carboxymethylcellulose with 80:10:10 mass ratio mixing, use deionized water for dispersing agent, said mixture mixed
Conjunction is uniformly tuned into slurry and is applied on copper foil, Na3V2(PO4)3As positive electrode active materials, positive electrode active materials and acetylene black are gathered partially
Vinyl fluoride is used 1 ~ methyl ~ 2 ~ pyrrolidones for dispersing agent, said mixture is uniformly mixed with the mixing of 80:10:10 mass ratio
It is tuned into slurry to be applied on aluminium foil, 60 DEG C of drying obtain corresponding cathode pole piece and anode pole piece after cutting out, and (positive electrode capacity is much larger than
The negative electrode tab capacity cut out), cathode pole piece is separated with positive plate using Whatman glass fibre membrane, 1 M is used
NaClO4Being dissolved in EC:PC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into as shell
CR2025 formula button cell, the sodium-ion battery that the above process is assembled at room temperature, charge and discharge in the potential range of 1.0 ~ 3.2 V
Electrical testing, charging and discharging curve are as shown in Figure 5.Second week charge specific capacity is 528.5 mA h/g, specific discharge capacity 482.5
MA h/g, coulombic efficiency are 91.3 %, 0.5 A g-1Material still maintains 415.6 mA h/g after 100 weeks circulations under current density
Capacity, capacity retention ratio be 86.8 %.
Embodiment 4
Carbon-coated ferrous sulfide agent particle size is 300 ~ 500nm in the present embodiment, and wherein the quality of clad is the material matter
The 15% of amount.
Carbon-coated ferrous sulfide material electrode material the preparation method is as follows:
(1) it weighs 0.96g green vitriol and 2.44g dissolution of ascorbic acid is stirred in 100mL deionized water
Presoma is made in -40 DEG C of freeze-drying 48h after even；
(2) the presoma grinding that step (1) obtains is placed on 800 DEG C of calcining 8h in the tube furnace of inert atmosphere, grinding system
Obtain carbon-coated ferrous sulfide substance.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (acetylene
It is black), gelatin with the mixing of 70:15:15 mass ratio, use deionized water for dispersing agent, be slurred said mixture is uniformly mixed
Material is applied on copper foil, cuts out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is (is much larger than electrode capacity and is cut to electrode
The negative electrode tab capacity of sanction), cathode pole piece is separated with metallic sodium piece using modified acetate fiber diaphragm, 1M NaPF is used6It is dissolved in
EC:DMC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into CR2025 formula button as shell
Battery, the battery that the above process is assembled at room temperature, charge-discharge test in the potential range of 0.3 ~ 2.5 V.
Embodiment 5
The preparation of the carbon-coated ferrous sulfide substance of the present embodiment is the same as embodiment 4.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (Super
P Li), sodium carboxymethylcellulose with 80:10:10 mass ratio mixing, use deionized water for dispersing agent, said mixture mixed
Conjunction is uniformly tuned into slurry and is applied on copper foil, Na2.4Fe1.8(SO4)3As positive electrode active materials, positive electrode active materials and acetylene black,
Kynoar is used 1-Methyl-2-Pyrrolidone for dispersing agent, said mixture is mixed with the mixing of 70:20:10 mass ratio
It is uniformly tuned into slurry and is applied on aluminium foil, 60 DEG C of drying obtain corresponding cathode pole piece and anode pole piece after cutting out (positive electrode capacity is remote
Greater than the negative electrode tab capacity cut out), cathode pole piece is separated with positive plate using Whatman glass fibre membrane, 1 M is used
NaClO4Being dissolved in EC:PC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into as shell
CR2025 formula button cell, the sodium-ion battery that the above process is assembled at room temperature, charge and discharge in the potential range of 1.0 ~ 3.2 V
Electrical testing.
Embodiment 6
Carbon-coated Fe in the present embodiment5Ni4S8Agent particle size is 300 ~ 500nm, and wherein the quality of clad is the quality of materials
3%, wherein doped chemical quality be the quality of materials 30%.
Carbon-coated Fe5Ni4S8Electrode material the preparation method is as follows:
(1) six ferrous sulfate hydrate ammonium of 0.68g, 0.46g six hydration nickel sulfate and 3.28g monohydrate potassium is weighed to be dissolved in
Presoma is made in -40 DEG C of freeze-drying 12h after being uniformly mixed in 100mL deionized water；
(2) the presoma grinding that step (1) obtains is placed on 700 DEG C of calcining 5h in the tube furnace of inert atmosphere, grinding system
Obtain carbon-coated Fe5Ni4S8Electrode material.
By prepared carbon-coated Fe5Ni4S8Electrode material is as negative electrode active material, negative electrode material and conductive charcoal
(Super P Li), sodium carboxymethylcellulose use deionized water for dispersing agent with the mixing of 70:15:15 mass ratio, will be above-mentioned mixed
It closes object and is uniformly mixed and be tuned into slurry and be applied on copper foil, cut out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is that negative electrode is (right
Electrode capacity is much larger than cut out negative electrode tab capacity), cathode pole piece is separated with metallic sodium piece using polypropylene diaphragm, is used
1 M NaCF3SO3Being dissolved in diethylene glycol dimethyl ether is electrolyte, and stainless steel steel shell is assembled into CR2025 formula button as shell
Battery, the battery that the above process is assembled at room temperature, charge-discharge test in the potential range of 0.3 ~ 2.5 V.
Embodiment 7
Ferrous sulfide 300 ~ 500nm of agent particle size of carbon-coated Copper-cladding Aluminum Bar in the present embodiment, wherein the quality of clad is to be somebody's turn to do
The 30% of quality of materials, wherein doped chemical quality is the 1.3% of the quality of materials.
The synthesis step of the ferrous sulfide substance of carbon-coated part Copper-cladding Aluminum Bar used in the present invention is as follows:
(1) 13.6g green vitriol, 29.1g monohydrate potassium and 0.3g Salzburg vitriol are weighed, is dissolved in
Presoma is made after being uniformly mixed in 1000mL deionized water after -40 DEG C of freeze-drying 12h；
(2) the presoma grinding that step (1) obtains is placed on 850 DEG C of calcining 2h in the tube furnace of inert atmosphere, grinding system
The ferrous sulfide substance of carbon-coated part Copper-cladding Aluminum Bar must be made.
Using the ferrous sulfide substance of prepared carbon-coated part Copper-cladding Aluminum Bar as negative electrode active material, negative electrode material with
Conductive charcoal (acetylene black), polytetrafluoroethylene (PTFE) use isopropanol for dispersing agent, by said mixture with the mixing of 80:10:10 mass ratio
It is uniformly mixed and is tuned into slurry and is applied on copper foil, cut out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is to electrode (to electrode
Capacity is much larger than cut out negative electrode tab capacity), cathode pole piece is separated with metallic sodium piece using polyethylene diagrams, 1 M is used
NaPF6Being dissolved in EC:DMC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into as shell
CR2025 formula button cell, the battery that the above process is assembled at room temperature, charge and discharge electrical measurement in the potential range of 0.01 ~ 2.5 V
Examination.
Embodiment 8
Carbon-coated ferrous sulfide material grains 300 ~ 500nm of partial size in the present embodiment, wherein the quality of clad is the material
The 20% of quality.
The synthesis step of carbon-coated ferrous sulfide substance used in the present invention is as follows:
(1) 0.45g green vitriol, six ferrous sulfate hydrate ammonia of 1.36g and 3.82g monohydrate potassium is weighed to be dissolved in
Presoma is made after being uniformly mixed in 100mL deionized water after -50 DEG C of freeze-drying 16h；
(2) the presoma grinding that step (1) obtains is placed on 850 DEG C of calcining 2h in the tube furnace of inert atmosphere, grinding system
Carbon-coated ferrous sulfide substance must be made.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (acetylene
It is black), polyacrylic acid with the mixing of 75:15:10 mass ratio, use ethyl alcohol for dispersing agent, be slurred said mixture is uniformly mixed
Material is applied on copper foil, cuts out to obtain cathode pole piece after 60 DEG C of drying, metallic sodium piece is (is much larger than electrode capacity and is cut to electrode
The negative electrode tab capacity of sanction), cathode pole piece is separated with metallic sodium piece using modified acetate fiber diaphragm, 1 M NaPF is used6It is molten
In EC:DMC(volume ratio be 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into CR2025 formula knob as shell
Detain battery, the battery that the above process is assembled at room temperature, charge-discharge test in the potential range of 0.3 ~ 2.5 V.
Embodiment 9
The preparation of the carbon-coated ferrous sulfide substance of the present embodiment is the same as embodiment 8.
Using prepared carbon-coated ferrous sulfide substance as negative electrode active material, negative electrode material and conductive charcoal (Super
P Li), sodium carboxymethylcellulose with 85:5:10 mass ratio mixing, use deionized water for dispersing agent, said mixture mixed
It is uniformly tuned into slurry to be applied on copper foil, Na0.44MnO2As positive electrode active materials, positive electrode active materials and acetylene black, polyvinylidene fluoride
Alkene uses 1-Methyl-2-Pyrrolidone for dispersing agent with the mixing of 80:10:10 mass ratio, and said mixture is uniformly mixed and is tuned into
Slurry is applied on aluminium foil, and 60 DEG C of drying obtain corresponding cathode pole piece and anode pole piece after cutting out (positive electrode capacity is much larger than being cut
The negative electrode tab capacity of sanction), cathode pole piece is separated with positive plate using Whatman glass fibre membrane, 1 M NaPF6It is dissolved in EC:
DMC(volume ratio is 1:1) (FEC additive) be electrolyte, stainless steel steel shell is assembled into CR2025 formula button electricity as shell
Pond, the sodium-ion battery that the above process is assembled at room temperature, charge-discharge test in the potential range of 0.8 ~ 3.5 V.
Embodiment 10
Carbon-coated ferrous sulfide agent particle size is 100 ~ 200nm in the present embodiment, and wherein the quality of clad is the material matter
The 10% of amount.
The synthesis step of carbon-coated ferrous sulfide substance used in the present invention is as follows:
(1) it weighs 0.96 g green vitriol and 0.96 g glucose is dissolved in 3.84 mL deionized waters and is stirred
Presoma uniformly is made after rear ~ 50 DEG C of freeze-drying 6h；
(2) the presoma grinding that step (1) obtains is placed on 500 DEG C of calcinings in the tube furnace of inert atmosphere and for 24 hours, grinds system
Obtain carbon-coated ferrous sulfide substance.
Embodiment 11
Carbon-coated ferrous sulfide agent particle size is 300 ~ 500nm in the present embodiment, and wherein the quality of clad is the material matter
The 15% of amount.
The synthesis step of carbon-coated ferrous sulfide substance used in the present invention is as follows:
(1) it weighs 0.96 g green vitriol and 9.6 g monohydrate potassiums is dissolved in 960 mL deionized waters and stirs
Presoma is made after -40 DEG C of freeze-drying 60h after mixing；
(2) the presoma grinding that step (1) obtains is placed on 600 DEG C of calcining 12h in the tube furnace of inert atmosphere, grinding system
Obtain carbon-coated ferrous sulfide substance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of carbon-coated ferrous sulfide negative electrode material, it is characterised in that: negative electrode material is carbon-coated ferrous sulfide material,
The quality of carbon coating layer is the 3% ~ 30% of cathode quality of materials, and ferrous sulfide grain diameter is 100 ~ 500nm.
2. the carbon-coated ferrous sulfide negative electrode material of sodium-ion battery according to claim 1, it is characterised in that: described negative
Also contain doping and modification element in the material of pole, doping and modification element be one of Co, Ni, Mn, Ti, Cu, Mg, Ba, Pb, Al or
It is several；The quality of carbon coating layer is the 3% ~ 30% of cathode quality of materials in negative electrode material, and the quality of doping and modification element is cathode
The 0 ~ 30% of quality of materials.
3. the preparation method of carbon-coated ferrous sulfide negative electrode material of any of claims 1 or 2, it is characterised in that step is such as
Under:
(1) carbon source and ferrous sulfate or doping metals sulfate are dissolved in deionized water, after being uniformly mixed in -40 ~
Presoma is made in -56 DEG C of 6 ~ 60h of freeze-drying；
(2) after the grinding of presoma that step (1) obtains being placed on 500 ~ 850 DEG C of calcinings 1 in the tube furnace of inert atmosphere ~ for 24 hours
Obtain carbon-coated ferrous sulfide negative electrode material.
4. the preparation method of carbon-coated ferrous sulfide negative electrode material according to claim 3, it is characterised in that: the step
Suddenly the mass ratio of carbon source in (1), ferrous sulfate, doping metals sulfate and deionized water is (1 ~ 10): 1:(0 ~ 1): (4 ~
1000).
5. the preparation method of carbon-coated ferrous sulfide negative electrode material according to claim 3, it is characterised in that: the step
Suddenly carbon source is one or more of citric acid, ascorbic acid, glucose in (1)；Doping metals sulfate be iron ammonium sulfate,
One or more of cobaltous sulfate, nickel sulfate, manganese sulfate, titanium sulfate, copper sulphate, magnesium sulfate, barium sulfate, lead sulfate, aluminum sulfate.
6. the sodium-ion battery of carbon-coated ferrous sulfide negative electrode material preparation described in claim 1, including positive plate, cathode
Piece, electrolyte, diaphragm and shell, it is characterised in that: sodium-ion battery using can embedding removing sodium active material as positive electrode, carbon
The ferrous sulfide of cladding is negative electrode material, and diaphragm is that fibreglass diaphragm, polypropylene diaphragm, polyethylene diagrams and modified acetic acid are fine
One or more of plain diaphragm is tieed up, soluble sodium salt organic solution is electrolyte.
7. the sodium-ion battery of carbon-coated ferrous sulfide negative electrode material preparation according to claim 6, it is characterised in that:
It is described can embedding removing sodium active material be Na3V2(PO4)3、Na3V2(PO4)2F3、NaFePO4、NaMnO2、NaFeO2、FePO4、
Na2.4Fe1.8(SO4)3、Na4Fe(CN)6、Na4Co3(PO4)2P2O7One of electrode material is several.
8. the sodium-ion battery of carbon-coated ferrous sulfide negative electrode material preparation according to claim 6, it is characterised in that:
The soluble sodium salt organic solution is that sodium salt is dissolved in organic solvent and obtaining, the sodium salt be sodium hexafluoro phosphate, sodium perchlorate,
The one or more of trifluoromethyl sulfonate and bis trifluoromethyl sulfimide sodium, organic solvent are ethylene carbonate, carbonic acid third
One or more of enester, diethyl carbonate, diethylene glycol dimethyl ether and triglyme.
9. the sodium-ion battery of carbon-coated ferrous sulfide negative electrode material preparation according to claim 6, it is characterised in that:
The positive plate and negative electrode tab pass through positive electrode and negative electrode material and conductive agent, binder and dispersing agent after evenly mixing respectively
Obtained slurry full-filling is obtained to collector, and collector is carbon cloth, metal stainless steel, nickel and aluminium it is porous, netted or thin
Membrane material；The conductive agent is one or more of acetylene black, carbon black, graphite or Super P Li；Binder is poly- four
Vinyl fluoride, Kynoar, sodium carboxymethylcellulose, polyacrylic acid, polyvinylidene fluoride, sodium alginate, gelatin or butylbenzene rubber
One or more of glue；Dispersing agent is one or more of water, ethyl alcohol, isopropanol or 1-Methyl-2-Pyrrolidone.
10. the sodium-ion battery of carbon-coated ferrous sulfide negative electrode material preparation according to claim 6, feature exist
In: the shell uses organic plastics, aluminum hull, aluminum plastic film, stainless steel and its composite material, and shape is button, column or rectangular.
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