CN109713313A - A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell - Google Patents
A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell Download PDFInfo
- Publication number
- CN109713313A CN109713313A CN201811641940.3A CN201811641940A CN109713313A CN 109713313 A CN109713313 A CN 109713313A CN 201811641940 A CN201811641940 A CN 201811641940A CN 109713313 A CN109713313 A CN 109713313A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulphur
- carbon
- positive electrode
- transition metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell, the positive plate includes the painting cream of collector and coating on a current collector, the painting cream includes active carbon, carbon black, transition metal, sulphur, conductive agent and binder, active carbon, carbon black, transition metal, sulphur, conductive agent and binder mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.The sulphur is present in the hole of active carbon and carbon black.Active carbon is as the main body for carrying sulphur, carbon black can either carry out load sulphur, also it can reinforce the electric conductivity of positive electrode, transition metal or transistion metal compound can play fixed function to the more lithium sulfides generated in electrochemical reaction, the shuttle effect for inhibiting more sulphions, improves the cycle performance of lithium-sulfur cell.Lithium sulfur battery anode material disclosed by the invention, have many advantages, such as simplicity be easy to get, be easy large scale preparation, available long circulating, height ratio capacity, high-energy-density lithium-sulfur cell.
Description
Technical field
The invention belongs to lithium-sulfur cell technical fields, and in particular to a kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium
Sulphur battery.
Background technique
Lithium-sulfur cell includes the anode containing electroactive sulfur, the cathode containing lithium, electrolyte and diaphragm.Lithium-sulfur cell theory ratio
Energy is up to 2600 Wh/kg, and practical specific energy is higher than current commercial li-ion battery.This is significant on specific energy
Advantage, so that lithium-sulfur cell, in special power supply, electric car and high-altitude vehicle etc. have extensive potential application.
The anode of lithium-sulfur cell is the important component and key technology of lithium-sulfur cell.Anode is by two parts (collector
With painting cream) composition, it is the field that electrochemical reaction occurs that collector, which plays the role of conducting electronics, applies cream and contain active material sulphur,
Institute.In the electrochemical reaction for applying cream part, the participation of lithium ion was both needed, while being also required to the conduction of electronics.In general, sulphur
It needs to carry out compound, raising electric conductivity with porous carbon, can there is better capacity performance.Active carbon as carbon material one
Kind, cheap with biomass (such as sawdust, charcoal, cocoanut shell etc.) for raw material, density is high, mature production technology, but conductive
Property is slightly worse.Carrier of the active carbon as sulphur, so that the capacity performance of lithium-sulfur cell is not ideal enough.Therefore, such as how active carbon is made
For the main body for carrying sulphur, the capacity for improving lithium-sulfur cell is played, and obtains the excellent lithium-sulphur cell positive electrode of various aspects of performance, has important
Practical application value.
Summary of the invention
The purpose of the invention is to obtain high capacity to play, macrocyclic lithium-sulphur cell positive electrode provides a kind of lithium sulphur electricity
Pond positive plate and preparation method thereof and lithium-sulfur cell.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of lithium-sulphur cell positive electrode piece, the positive plate include the painting cream of collector and coating on a current collector, the painting
Cream include active carbon, carbon black, transition metal, sulphur, conductive agent and binder, active carbon, carbon black, transition metal, sulphur, conductive agent and
The mass ratio of binder is 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
A kind of preparation method of above-mentioned lithium-sulphur cell positive electrode piece, it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, forced air drying grind and are sieved, and 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container, grinds and is sieved,
Obtain carbon-sulfur compound；Shape in deionized water is dispersed by above-mentioned carbon-sulfur compound and transition metal, conductive agent and binder
At slurry, slurry is coated on a current collector, and then heating, drying obtains lithium-sulphur cell positive electrode piece.
A kind of lithium-sulfur cell containing above-mentioned lithium-sulphur cell positive electrode piece, the lithium-sulfur cell be include positive plate,
The laminated batteries of negative electrode tab, diaphragm and electrolyte；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is polyene
Hydrocarbon porous septum；The electrolyte is ethers electrolyte.
A kind of lithium-sulphur cell positive electrode piece, the positive plate includes the painting cream of collector and coating on a current collector, described
Painting cream include active carbon, carbon black, transistion metal compound, sulphur, conductive agent and binder, active carbon, carbon black, transition metal
The mass ratio for closing object, sulphur, conductive agent and binder is 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
A kind of a kind of preparation method of above-mentioned lithium-sulphur cell positive electrode piece, it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, forced air drying grind and are sieved, and 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container, grinds and is sieved,
Obtain carbon-sulfur compound；Deionization is dispersed by above-mentioned carbon-sulfur compound and transistion metal compound, conductive agent and binder
Slurry is formed in water, slurry is coated on a current collector, and then heating, drying obtains lithium-sulphur cell positive electrode piece.
A kind of lithium-sulfur cell containing above-mentioned lithium-sulphur cell positive electrode piece, the lithium-sulfur cell be include positive plate,
The laminated batteries of negative electrode tab, diaphragm and electrolyte；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is polyene
Hydrocarbon porous septum；The electrolyte is ethers electrolyte.
The beneficial effect of the present invention compared with the existing technology is:
Positive plate of the invention is had excellent performance, and active carbon with high specific surface area adds a certain amount of high-ratio surface as the main body for carrying sulphur
Carbon deposit black-materials, and a certain amount of transition metal or transistion metal compound is added, the appearance of lithium-sulfur cell can be effectively improved
Amount plays and cyclical stability.Due to the high-specific surface area of carbon black, carbon black not only plays enhancing electric conductivity in compound system
Effect, while also as the carrier of sulphur, it is ensured that higher load sulphur specific gravity solves merely using active carbon as the carbon sulphur of carrier
The weakness of composite conductivity difference.Metal or metallic compound can play fixed work to the more lithium sulfides of electrochemistry intermediate product
With, inhibit the shuttle effect of more sulphions, effectively improve lithium-sulfur cell capacity play and cyclical stability.
Specific embodiment
Below with reference to embodiment, further description of the technical solution of the present invention, and however, it is not limited to this, all right
Technical solution of the present invention is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be contained
Lid is within the protection scope of the present invention.Reagent, material and the instrument arrived used in following the description such as not special explanation,
It is conventional reagent, conventional material and conventional instrument, commercially available, related reagent can also be by the side of being conventionally synthesized
Method synthesis obtains.
Specific embodiment 1: present embodiment record is a kind of lithium-sulphur cell positive electrode piece, the positive plate includes
The painting cream of collector and coating on a current collector, wherein applying the surface density of cream on a current collector is 1 ~ 20 mg/cm2, described
Applying cream includes active carbon, carbon black, transition metal, sulphur, conductive agent and binder, active carbon, carbon black, transition metal, sulphur, conductive agent
Mass ratio with binder is 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
Specific embodiment 2: a kind of lithium-sulphur cell positive electrode piece, the collector described in specific embodiment one are
Aluminium foil or utter misery aluminium foil；The specific surface area of the active carbon is 500 ~ 3000 m2/g；The specific surface area of the carbon black is
500~3000 m2/g；The transition metal be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag,
Pt, group of the lanthanides or actinide metals；The sulphur is present in the hole of active carbon and carbon black.
Specific embodiment 3: a kind of lithium-sulphur cell positive electrode piece, the transition described in specific embodiment one or two
The particle diameter of metal is less than 1 micron, preferably several hundred nanometers, and optimal is tens or several nanometers.
Specific embodiment 4: a kind of lithium sulphur described in any specific embodiment in a kind of specific embodiment one to three
The preparation method of battery anode slice, it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, 60 ~ 100oC forced air drying 6 ~ for 24 hours, it grinds and is sieved, 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container,
It grinds and is sieved to get carbon-sulfur compound is arrived；The mesh number of sieve used is 50 ~ 300 mesh；Described is ground to hand lapping or machine
Tool ball milling；Slurry is formed and is dispersed above-mentioned carbon-sulfur compound and transition metal, conductive agent and binder in deionized water, slurry
Solid content be 20% ~ 50%, slurry is coated on a current collector, then 60 ~ 100oC, which heats 3 ~ 48 h, is drying to obtain lithium-sulfur cell just
Pole piece.
Specific embodiment 5: a kind of contain lithium sulphur described in specific embodiment any in specific embodiment one to three
The lithium-sulfur cell of battery anode slice, the lithium-sulfur cell are the laminated battery for including positive plate, negative electrode tab, diaphragm and electrolyte
Pond；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is polyolefin porous separator；The electrolyte is ethers
Electrolyte.
Specific embodiment 6: present embodiment record is a kind of lithium-sulphur cell positive electrode piece, the positive plate includes
The painting cream of collector and coating on a current collector, wherein applying the surface density of cream on a current collector is 1 ~ 20 mg/cm2, described
Applying cream includes active carbon, carbon black, transistion metal compound, sulphur, conductive agent and binder, active carbon, carbon black, transition metal compound
Object, sulphur, conductive agent and binder mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
Specific embodiment 7: a kind of lithium-sulphur cell positive electrode piece, the collector described in specific embodiment six are
Aluminium foil or utter misery aluminium foil；The specific surface area of the active carbon is 500 ~ 3000 m2/g；The specific surface area of the carbon black is
500~3000 m2/g；The transistion metal compound is transition metal carbide, transition metal boride, transition metal nitrogen
Compound, transition metal phosphide, one of transition metal oxide and transient metal sulfide or a variety of；The sulphur exists
In the hole of active carbon and carbon black.
Specific embodiment 8: a kind of lithium-sulphur cell positive electrode piece described in specific embodiment six or seven, the transition gold
Belong to the particle diameter of compound less than 1 micron, preferably several hundred nanometers, optimal is tens or several nanometers.
Specific embodiment 9: a kind of lithium-sulphur cell positive electrode piece, the transition metal described in specific embodiment seven
Carbide is TiC, Ti2C, Nb4C3, Ti3C2, V3C2, Cr3C2, Mo2TiC2, Mo2Ti2C3, V2C, Nb2C, V8C7, MoC, WC, ZrC,
Mo2C, VC, Fe3One of C or a variety of；The transition metal boride is Ni-B, Co-B, Fe-B, Ru-B, Pd-B, Ti-
One of B, Cr-B, Zr-B or a variety of；The transition metal nitride is WN, VN, TiN, W2N, LaN, Mo2One of N
Or it is a variety of；The transition metal phosphide is Zn3P2, Cu3P2, Fe3P2, Co2P, FeP, Ni12P5, Ni2P, Ni5P4, CoP,
Cu3P, Mo3P, MoP, MoP2, one of WP or a variety of；The transition metal oxide is MnO2, Fe2O3, Ti4O7,
La2O3, TiO2, MoO3, ZrO2, one of NiO or a variety of；The transient metal sulfide is Co9S8, Co3S4, CoS2,
FeS2, TiS2, MnS, CuS, ZnS, SnS2, NiS2, ZrS2, VS2, MoS2One of or it is a variety of.
Specific embodiment 10: a kind of lithium sulphur described in any specific embodiment in a kind of specific embodiment six to nine
The preparation method of battery anode slice, it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, 60 ~ 100oC forced air drying 6 ~ for 24 hours, it grinds and is sieved, 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container,
It grinds and is sieved to get carbon-sulfur compound is arrived；The mesh number of sieve used is 50 ~ 300 mesh；Described is ground to hand lapping or machine
Tool ball milling；It disperses above-mentioned carbon-sulfur compound and transistion metal compound, conductive agent and binder in deionized water and forms slurry
Material, the solid content of slurry are 20% ~ 50%, and slurry is coated on a current collector, then 60 ~ 100oC, which heats 3 ~ 48 h, dries to obtain lithium
Sulphur cell positive electrode piece.
Specific embodiment 11: a kind of to contain lithium described in specific embodiment any in specific embodiment six to nine
The lithium-sulfur cell of sulphur cell positive electrode piece, the lithium-sulfur cell are the lamination for including positive plate, negative electrode tab, diaphragm and electrolyte
Battery；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is polyolefin porous separator；The electrolyte is ether
Class electrolyte.
Embodiment 1:
By active carbon (2100 m2/ g, 20 parts of quality) and carbon black (1830 m2/ g, 10 parts of quality) mixing, grinding, until mixing
Object can all be sieved, then be mixed with sulphur (70 parts of quality), and grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids not to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
140oC heats 24 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
With cobalt nano-particle (3 parts of quality), conductive agent (Super P, 5 parts of quality) and binder (CMC/SBR of 1:1,5 parts of quality) point
It dissipating and forms slurry in deionized water, slurry is coated on utter misery aluminium foil, and then 60oC heats 48 h drying, obtains lithium-sulfur cell
(load sulfur content is 3.5 mg/cm to positive plate2), it is named as Z1.
Comparative example 1-1:
Places comparative example 1-1 different from embodiment 1 are, are added without Co nano particle.
Comparative example 1-2:
Places comparative example 1-1 different from embodiment 1 are, are added without carbon black.
Comparative example 1-3:
Places comparative example 1-1 different from embodiment 1 are, are added without Co nano particle and carbon black.
Embodiment 2:
By active carbon (2950 m2/ g, 10 parts of quality) and carbon black (530 m2/ g, 1 part of quality) mixing, grinding, until mixture
It can all be sieved, then be mixed with sulphur (50 parts of quality), grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
300oC heats 3 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition and
Fe3C nano particle (1 part of quality) and binder (CMC/SBR of 1:1,1 part of quality) are scattered in deionized water and form slurry,
Slurry is coated on utter misery aluminium foil, and then 100oC heats 3 h drying, and obtaining lithium-sulphur cell positive electrode piece, (load sulfur content is 3.5 mg/
cm2), it is named as Z2.
Comparative example 2-1:
Places comparative example 2-1 different from embodiment 2 are, are added without Fe3C nano particle.
Embodiment 3:
By active carbon (620 m2/ g, 10 parts of quality) and carbon black (2890 m2/ g, 10 parts of quality) mixing, grinding, until mixture
It can all be sieved, then be mixed with sulphur (50 parts of quality), grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
155oC heats 12 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
And Ni2B nano particle (10 parts of quality), conductive agent (MWCNT, 10 parts of quality) and binder (CMC/SBR of 2:1,10 parts of matter
Amount) it is scattered in deionized water and forms slurry, slurry is coated on utter misery aluminium foil, and then 80oC heats 10 h drying, obtains lithium
(load sulfur content is 3.5 mg/cm to sulphur cell positive electrode piece2), it is named as Z3.
Comparative example 3-1:
Places comparative example 3-1 different from embodiment 3 are, are added without Ni2B nano particle.
Embodiment 4:
By active carbon (1480 m2/ g, 20 parts of quality) and carbon black (1450 m2/ g, 10 parts of quality) mixing, grinding, until mixing
Object can all be sieved, then be mixed with sulphur (80 parts of quality), and grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids not to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
170oC heats 24 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
With TiN nano particle (5 parts of quality), conductive agent (Super P, 5 parts of quality) and binder (CMC/SBR of 1:1,5 parts of quality)
It being scattered in deionized water and forms slurry, slurry is coated on utter misery aluminium foil, and then 80oC heats 12 h drying, obtains lithium sulphur electricity
(load sulfur content is 3.5 mg/cm to pond positive plate2), it is named as Z4.
Comparative example 4-1:
Places comparative example 4-1 different from embodiment 4 are, are added without TiN nano particle.
Comparative example 4-2:
Places comparative example 4-2 different from embodiment 4 are, are added without carbon black.
Comparative example 4-3:
Places comparative example 4-3 different from embodiment 4 are, are added without TiN nano particle and carbon black.
Embodiment 5:
By active carbon (1480 m2/ g, 30 parts of quality) and carbon black (1450 m2/ g, 10 parts of quality) mixing, grinding, until mixing
Object can all be sieved, then be mixed with sulphur (80 parts of quality), and grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids not to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
155oC heats 12 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
It is scattered in WP nano particle (5 parts of quality), conductive agent (Super P, 5 parts of quality) and binder (LA133,5 parts of quality)
Slurry is formed in ionized water, slurry is coated on aluminium foil, and then 80oC heats 12 h drying, obtains lithium-sulphur cell positive electrode piece and (carries
Sulfur content is 6.2 mg/cm2), it is named as Z5.
Comparative example 5-1:
Places comparative example 5-1 different from embodiment 5 are, are added without WP nano particle.
Embodiment 6:
By active carbon (1480 m2/ g, 20 parts of quality) and carbon black (1450 m2/ g, 10 parts of quality) mixing, grinding, until mixing
Object can all be sieved, then be mixed with sulphur (80 parts of quality), and grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids not to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
160oC heats 24 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
And MnO2Nano particle (5 parts of quality), conductive agent (Super P, 5 parts of quality) and binder (CMC/SBR of 1:1,5 parts of quality)
It being scattered in deionized water and forms slurry, slurry is coated on utter misery aluminium foil, and then 70oC heats 20 h drying, obtains lithium sulphur electricity
(load sulfur content is 6.2 mg/cm to pond positive plate2), it is named as Z6.
Comparative example 6-1:
Places comparative example 6-1 different from embodiment 6 are, are added without MnO2Nano particle.
Embodiment 7:
By active carbon (1480 m2/ g, 20 parts of quality) and carbon black (1450 m2/ g, 10 parts of quality) mixing, grinding, until mixing
Object can all be sieved, then be mixed with sulphur (80 parts of quality), and grinding enables mixture to be all sieved, and carbon disulfide is added to flood
The surface of solids not to be crossed, is stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is dry, and it grinds and is sieved,
140oC heats 24 h in closed container, grinds and is sieved to get carbon-sulfur compound is arrived；By the carbon-sulfur compound of above-mentioned acquisition
And VS2Nano particle (5 parts of quality), conductive agent (Super P, 5 parts of quality) and binder (CMC/SBR of 1:1,5 parts of quality)
It being scattered in deionized water and forms slurry, slurry is coated on utter misery aluminium foil, and then 80oC heats 10 h drying, obtains lithium sulphur electricity
(load sulfur content is 6.2 mg/cm to pond positive plate2), it is named as Z7.
Comparative example 7-1:
Places comparative example 7-1 different from embodiment 7 are, are added without VS2Nano particle.
Lithium-sulfur cell Integration Assembly And Checkout: by the above positive plate and cathode (metallic lithium foil) and electrolyte (1 M LiTFSI
It is dissolved in the DOL/DME in the mixed solvent of volume ratio 1:1, additive is 0.2M LiNO3) be assembled into laminated batteries, electrolyte and
The mass ratio of sulphur is 3.5, charge-discharge test (0.2C/0.2C) is carried out with battery test apparatus, to the initial of each positive electrode
Gram volume and cycle performance (60% cycle-index that capacity is reduced to first capacity) are compared.Obtained data such as table 1
It is shown.It can be seen that anode of the invention from the battery performance of the obtained positive electrode of each embodiment and comparative example in table 1
Piece can obtain higher gram volume and preferable cycle performance.Carbon black and metal or metallic compound in positive electrode
Component effectively improves the poor defect of active carbon electric conductivity, and improves the problems of dissolution of more sulphions, is conducive to gram volume
Performance and obtain more preferably cycle performance.
Claims (11)
1. a kind of lithium-sulphur cell positive electrode piece, it is characterised in that: the positive plate includes collector and coats on a current collector
Cream is applied, the painting cream includes active carbon, carbon black, transition metal, sulphur, conductive agent and binder, active carbon, carbon black, transition gold
Category, sulphur, conductive agent and binder mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
2. a kind of lithium-sulphur cell positive electrode piece according to claim 1, it is characterised in that: the collector is aluminium foil or painting
Charcoal aluminium foil；The specific surface area of the active carbon is 500 ~ 3000 m2/g；The specific surface area of the carbon black is 500 ~ 3000
m2/g；The transition metal be Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Ru, Rh, Pd, Ag, Pt, group of the lanthanides or
Actinide metals；The sulphur is present in the hole of active carbon and carbon black.
3. a kind of lithium-sulphur cell positive electrode piece according to claim 1 or 2, it is characterised in that: of the transition metal
Grain diameter is less than 1 micron.
4. a kind of preparation method of lithium-sulphur cell positive electrode piece, feature described in any claim in a kind of claim 1 ~ 3
Be: it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, forced air drying grind and are sieved, and 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container, grinds and is sieved,
Obtain carbon-sulfur compound；Shape in deionized water is dispersed by above-mentioned carbon-sulfur compound and transition metal, conductive agent and binder
At slurry, slurry is coated on a current collector, and then heating, drying obtains lithium-sulphur cell positive electrode piece.
5. lithium-sulfur cell of the one kind containing lithium-sulphur cell positive electrode piece described in any claim in claim 1 ~ 3, feature
Be: the lithium-sulfur cell is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；The negative electrode tab
Contain lithium metal or lithium alloy；The diaphragm is polyolefin porous separator；The electrolyte is ethers electrolyte.
6. a kind of lithium-sulphur cell positive electrode piece, it is characterised in that: the positive plate includes collector and coats on a current collector
Apply cream, the painting cream include active carbon, carbon black, transistion metal compound, sulphur, conductive agent and binder, active carbon, carbon black,
Transistion metal compound, sulphur, conductive agent and binder mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:50 ~ 80:0 ~ 10:1 ~ 10.
7. a kind of lithium-sulphur cell positive electrode piece according to claim 6, it is characterised in that: the collector is aluminium foil or painting
Charcoal aluminium foil；The specific surface area of the active carbon is 500 ~ 3000 m2/g；The specific surface area of the carbon black is 500 ~ 3000
m2/g；The transistion metal compound is transition metal carbide, transition metal boride, transition metal nitride, transition
Metal phosphide, one of transition metal oxide and transient metal sulfide or a variety of；The sulphur is present in active carbon
In the hole of carbon black.
8. a kind of lithium-sulphur cell positive electrode piece according to claim 6 or 7, it is characterised in that: the transistion metal compound
Particle diameter less than 1 micron.
9. a kind of lithium-sulphur cell positive electrode piece according to claim 7, it is characterised in that: the transition metal carbide is
TiC, Ti2C, Nb4C3, Ti3C2, V3C2, Cr3C2, Mo2TiC2, Mo2Ti2C3, V2C, Nb2C, V8C7, MoC, WC, ZrC, Mo2C, VC,
Fe3One of C or a variety of；The transition metal boride be Ni-B, Co-B, Fe-B, Ru-B, Pd-B, Ti-B, Cr-B,
One of Zr-B or a variety of；The transition metal nitride is WN, VN, TiN, W2N, LaN, Mo2One of N or a variety of；
The transition metal phosphide is Zn3P2, Cu3P2, Fe3P2, Co2P, FeP, Ni12P5, Ni2P, Ni5P4, CoP, Cu3P, Mo3P,
MoP, MoP2, one of WP or a variety of；The transition metal oxide is MnO2, Fe2O3, Ti4O7, La2O3, TiO2,
MoO3, ZrO2, one of NiO or a variety of；The transient metal sulfide is Co9S8, Co3S4, CoS2, FeS2, TiS2,
MnS, CuS, ZnS, SnS2, NiS2, ZrS2, VS2, MoS2One of or it is a variety of.
10. a kind of preparation method of lithium-sulphur cell positive electrode piece, feature described in any claim in a kind of claim 6 ~ 9
Be: it is described the preparation method is as follows:
Active carbon and carbon black are mixed, grinding, until mixture can all be sieved, then is mixed with sulphur, grinding makes to mix
Object can all be sieved, and carbon disulfide is added to flood the surface of solids, be stored at room temperature until carbon disulfide volatilization is clean, remove surface
The sulphur of precipitation, forced air drying grind and are sieved, and 120 ~ 300oC is placed on 3 ~ 24 h of heating in closed container, grinds and is sieved,
Obtain carbon-sulfur compound；Deionization is dispersed by above-mentioned carbon-sulfur compound and transistion metal compound, conductive agent and binder
Slurry is formed in water, slurry is coated on a current collector, and then heating, drying obtains lithium-sulphur cell positive electrode piece.
11. lithium-sulfur cell of the one kind containing lithium-sulphur cell positive electrode piece described in any claim in claim 6 ~ 9, feature
Be: the lithium-sulfur cell is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；The negative electrode tab
Contain lithium metal or lithium alloy；The diaphragm is polyolefin porous separator；The electrolyte is ethers electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811641940.3A CN109713313B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive plate and preparation method thereof and lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811641940.3A CN109713313B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive plate and preparation method thereof and lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109713313A true CN109713313A (en) | 2019-05-03 |
| CN109713313B CN109713313B (en) | 2020-10-09 |
Family
ID=66260413
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811641940.3A Active CN109713313B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive plate and preparation method thereof and lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713313B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818035A (en) * | 2019-12-16 | 2020-02-21 | 嘉兴市众盛环保科技有限公司 | TiN/activated carbon three-dimensional particle electrode and preparation method thereof |
| CN112701290A (en) * | 2020-12-29 | 2021-04-23 | 西安交通大学 | Lithium ion battery anode with titanium suboxide as additive, battery and preparation method |
| CN113823787A (en) * | 2021-08-17 | 2021-12-21 | 华南理工大学 | Porous sulfur composite cathode material and preparation method and application thereof |
| CN114597411A (en) * | 2022-03-02 | 2022-06-07 | 陕西科技大学 | Acetylene black flexible sulfur fixation material, preparation method thereof, sulfur fixation method and lithium-sulfur battery positive electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872299A (en) * | 2014-03-19 | 2014-06-18 | 陕西煤业化工技术研究院有限责任公司 | Element-doped oxide-sulfur composite material of positive electrode of lithium-sulfur battery and preparation method thereof |
| CN105742567A (en) * | 2016-04-27 | 2016-07-06 | 长沙矿冶研究院有限责任公司 | Composite positive electrode of lithium sulfur battery, preparation method of composite positive electrode and lithium sulfur battery |
| CN106684389A (en) * | 2016-12-30 | 2017-05-17 | 温州大学 | Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof |
| CN107959005A (en) * | 2017-10-25 | 2018-04-24 | 温州大学 | A kind of composite material of transient metal sulfide and graphene and preparation method and application |
-
2018
- 2018-12-29 CN CN201811641940.3A patent/CN109713313B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103872299A (en) * | 2014-03-19 | 2014-06-18 | 陕西煤业化工技术研究院有限责任公司 | Element-doped oxide-sulfur composite material of positive electrode of lithium-sulfur battery and preparation method thereof |
| CN105742567A (en) * | 2016-04-27 | 2016-07-06 | 长沙矿冶研究院有限责任公司 | Composite positive electrode of lithium sulfur battery, preparation method of composite positive electrode and lithium sulfur battery |
| CN106684389A (en) * | 2016-12-30 | 2017-05-17 | 温州大学 | Sulfur-nitrogen dual-doped graphene nano material and preparation method and application thereof |
| CN107959005A (en) * | 2017-10-25 | 2018-04-24 | 温州大学 | A kind of composite material of transient metal sulfide and graphene and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| 郑时有等: "过渡金属调制的碳／硫复合锂－硫电池正极材料", 《2017年锂硫电池前沿学术研讨会》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110818035A (en) * | 2019-12-16 | 2020-02-21 | 嘉兴市众盛环保科技有限公司 | TiN/activated carbon three-dimensional particle electrode and preparation method thereof |
| CN112701290A (en) * | 2020-12-29 | 2021-04-23 | 西安交通大学 | Lithium ion battery anode with titanium suboxide as additive, battery and preparation method |
| CN113823787A (en) * | 2021-08-17 | 2021-12-21 | 华南理工大学 | Porous sulfur composite cathode material and preparation method and application thereof |
| CN113823787B (en) * | 2021-08-17 | 2023-03-21 | 华南理工大学 | Porous sulfur composite cathode material and preparation method and application thereof |
| CN114597411A (en) * | 2022-03-02 | 2022-06-07 | 陕西科技大学 | Acetylene black flexible sulfur fixation material, preparation method thereof, sulfur fixation method and lithium-sulfur battery positive electrode |
| CN114597411B (en) * | 2022-03-02 | 2023-03-14 | 陕西科技大学 | Acetylene black flexible sulfur fixation material, preparation method thereof, sulfur fixation method and lithium-sulfur battery positive electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109713313B (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109713282B (en) | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery | |
| CN109713313A (en) | A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell | |
| Ihsan et al. | MoO2/Mo2C/C spheres as anode materials for lithium ion batteries | |
| CN105206841B (en) | A kind of pyrite class additive in lithium-sulphur cell positive electrode | |
| CN103493267B (en) | Electrode and electrical storage device for lead-acid system | |
| CN102569816B (en) | Positive electrode of lithium sulfur battery and preparation method thereof | |
| CN108232164A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN104956527B (en) | Transition metal hexacyanoferrate battery cathode, transition metal hexacyanoferrate cathode battery, method for synthesizing a transition metal hexacyanoferrate battery material, method for fabricating a transition metal hexacyanoferrate battery cathode electrode, and method for using a transition metal hexacyanoferrate battery | |
| CN105932242A (en) | Cathode material used for lithium-sulfur secondary battery | |
| CN108370024A (en) | High surface area porous carbon material as electrode | |
| KR20070057175A (en) | Battery positive electrode material containing sulfur and/or sulfur compound having s-s bond, and process for producing the same | |
| Zhang et al. | Pseudo-solid-solution CuCo2O4/C nanofibers as excellent anodes for lithium ion batteries | |
| CN105355925B (en) | A kind of preparation method of three-dimensional order nickel skeleton load germanium base lithium cell cathode material | |
| CN102593556A (en) | Lithium air or oxygen battery | |
| CN102157736A (en) | Ferrous disulfide/carbon composite cathode material of primary lithium battery and preparation method and application thereof | |
| CN109904455A (en) | A kind of lithium-sulphur cell positive electrode carrier material and preparation method thereof | |
| Song et al. | Hierarchical porous CoFe2O4/CoFe2Se4 nanosheet as supercapacitor electrodes: Effect of selenium content and pore structure on electrochemical performance | |
| CN109301254A (en) | A kind of lithium sulfur battery anode material, anode and its preparation and application | |
| Kulkarni et al. | Investigation of MnCo2O4/MWCNT composite as anode material for lithium ion battery | |
| Fei et al. | Controlling morphology and enhancing electrochemical performance of cobalt oxide by addition of graphite | |
| CN109713259A (en) | A kind of silicon-carbon composite cathode material of lithium ion battery and its preparation method and application | |
| Bai et al. | Bimetallic nanoparticles decorated porous carbon as the host material to enhance the performance of lithium-sulfur batteries | |
| JPH11345610A (en) | Negative electrode for battery and manufacture thereof | |
| CN109888254A (en) | A kind of zinc-base cell positive material based on aqueous solution, its preparation and application | |
| CN109103492A (en) | Hydroxyapatite nanowire-carbon nanotube film, preparation method thereof and lithium-sulfur battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant after: Zhuhai Guanyu Battery Co., Ltd Address before: 519180 No. 209 Pearl Peak Avenue, Jingan Town, Doumen District, Zhuhai City, Guangdong Province Applicant before: ZHUHAI COSLIGHT BATTERY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant |