CN109713282A - A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell - Google Patents
A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell Download PDFInfo
- Publication number
- CN109713282A CN109713282A CN201811642045.3A CN201811642045A CN109713282A CN 109713282 A CN109713282 A CN 109713282A CN 201811642045 A CN201811642045 A CN 201811642045A CN 109713282 A CN109713282 A CN 109713282A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sulphur
- coated
- anode material
- battery anode
- 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 sulfur battery anode material and preparation method thereof and lithium-sulfur cell, the positive electrode include active carbon, carbon black, transition metal or transistion metal compound and sublimed sulfur；The transistion metal compound is metal carbides, metal boride, metal nitride, metal phosphide, metal oxide or metal sulfide.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 sulfur battery anode material and preparation method thereof with
Lithium-sulfur cell.
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 positive electrode of lithium-sulfur cell is the key technology of lithium-sulfur cell.In general, sulphur needs and porous carbon is answered
It closes, improves electric conductivity, can there is better energy to play.The one kind of active carbon as carbon material with coke or naturally has
Machine plant such as charcoal or coconut husk etc. are raw material, and it is micron level that the particle of active carbon is larger, and specific surface area is higher, also has
It is cheap, the advantages of density is high, mature production technology, therefore active carbon can be used as the carrier material of sulphur, be applied to lithium sulphur
Battery.But the electric conductivity of absorbent charcoal material is poor, and the conductivity of sulphur is very low, uses active carbon as the lithium sulphur of sulfur-donor in this way
Anode, specific capacity and cycle performance are unsatisfactory.Especially in the case where height carries sulfur content and big multiplying power, the performance table of lithium-sulfur cell
It now can be worse.Therefore, if how active carbon is as carrying the main body of sulphur, while the capacity for improving lithium-sulfur cell plays, with important
Practical application value.
Summary of the invention
The present invention provides a kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cells, in order to solve
The composite conductivity of active carbon and sulphur difference and existing more sulphion problems of dissolution so as to cause circulating battery difference and
Capacity plays not ideal enough problem.
To achieve the above object, the technical solution adopted by the present invention is as follows:
A kind of lithium sulfur battery anode material, the positive electrode include active carbon, carbon black, transition metal and sulphur, active carbon, charcoal
The mass ratio of black, transition metal and sulphur is 10 ~ 30:1 ~ 10:1 ~ 10:60 ~ 80.
A kind of a kind of preparation method of above-mentioned lithium sulfur battery anode material, it is described the preparation method is as follows: by active carbon,
Carbon black and transition metal mixing, grinding until mixture can all be sieved, then are mixed with sulphur, and grinding enables mixture
Enough all sievings, add carbon disulfide to flood the surface of solids, are stored at room temperature until carbon disulfide volatilization is clean, removal surface is precipitated
Sulphur, 60 ~ 100oC forced air drying 6 ~ for 24 hours, it grinds and is sieved, 150 ~ 350oC is placed on 1 ~ 24 h of heating in closed container, grinding
And it is sieved to get lithium sulfur battery anode material is arrived；The mesh number of sieve used is 50 ~ 300 mesh；It is described be ground to hand lapping or
Mechanical ball mill.
A kind of lithium-sulfur cell of the lithium sulfur battery anode material containing above-mentioned preparation, the lithium-sulfur cell be include just
Pole piece, negative electrode tab, diaphragm and electrolyte laminated batteries；It is specific: the positive plate the preparation method comprises the following steps: by positive electrode,
Conductive agent, binder form slurry, the solid content of slurry according to the dispersion of 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio in deionized water
It is 20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heats 3 ~ 48 h drying, wherein slurry is applying
Surface density on charcoal aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is (1)
Polyolefin micropore barrier diaphragm substrate, (2) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer, (3) surface is coated with ceramics
Polyolefin micropore barrier diaphragm substrate or (4) surface be coated with polymer and ceramics polyolefin micropore barrier diaphragm substrate；The electricity
Solution liquid is ethers electrolyte.
A kind of lithium-sulfur cell containing above-mentioned lithium sulfur battery anode material, the lithium-sulfur cell be include anode
Piece, negative electrode tab, diaphragm and electrolyte laminated batteries；Specific: the positive plate is the preparation method comprises the following steps: by positive electrode, lead
Electric agent, binder form slurry according to the dispersion of 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio in deionized water, and the solid content of slurry is
20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heats 3 ~ 48 h drying, wherein slurry is in utter misery
Surface density on aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is poly- for (1)
Alkene micro-pore septum substrate, (2) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer, (3) surface is coated with ceramics
Polyolefin micropore barrier diaphragm substrate or (4) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer and ceramics；The electrolysis
Liquid is ethers electrolyte.
A kind of lithium sulfur battery anode material, the positive electrode include active carbon, carbon black, transistion metal compound and
Sulphur, active carbon, carbon black, transistion metal compound and sulphur mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:60 ~ 80.
A kind of a kind of preparation method of above-mentioned lithium sulfur battery anode material, it is described the preparation method is as follows: by active carbon,
Carbon black and transistion metal compound mixing, grinding until mixture can all be sieved, then are mixed with sulphur, and grinding makes to mix
Closing 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 table
The sulphur that face is precipitated, 60 ~ 100oC forced air drying 6 ~ for 24 hours, it grinds and is sieved, 150 ~ 350oC, which is placed in closed container, heats 1 ~ 24
H is ground and is sieved to get lithium sulfur battery anode material is arrived；The mesh number of sieve used is 50 ~ 300 mesh；Described is ground to craft
Grinding or mechanical ball mill.
A kind of lithium-sulfur cell of the lithium sulfur battery anode material containing above-mentioned preparation, the lithium-sulfur cell be include just
Pole piece, negative electrode tab, diaphragm and electrolyte laminated batteries；It is specific: the positive plate the preparation method comprises the following steps: by positive electrode,
Conductive agent, binder form slurry, the solid content of slurry according to the dispersion of 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio in deionized water
It is 20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heats 3 ~ 48 h drying, wherein slurry is applying
Surface density on charcoal aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is (1)
Polyolefin micropore barrier diaphragm substrate, (2) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer, (3) surface is coated with ceramics
Polyolefin micropore barrier diaphragm substrate or (4) surface be coated with polymer and ceramics polyolefin micropore barrier diaphragm substrate；The electricity
Solution liquid is ethers electrolyte.
A kind of lithium-sulfur cell containing above-mentioned lithium sulfur battery anode material, the lithium-sulfur cell be include positive plate,
The laminated batteries of negative electrode tab, diaphragm and electrolyte；Specific: the positive plate is the preparation method comprises the following steps: by positive electrode, conduction
Agent, binder form slurry according to the dispersion of 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio in deionized water, and the solid content of slurry is
20% ~ 50%, slurry is coated on utter misery aluminium foil, and then 60 ~ 100oC heats 3 ~ 48 h drying, wherein slurry is in utter misery aluminium
Surface density on foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium metal or lithium alloy；The diaphragm is (1) polyene
Hydrocarbon micro-pore septum substrate, (2) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer, (3) surface is coated with the poly- of ceramics
Alkene micro-pore septum substrate or (4) surface are coated with the polyolefin micropore barrier diaphragm substrate of polymer and ceramics；The electrolyte
For ethers electrolyte.
The beneficial effect of the present invention compared with the existing technology is: the present invention develops active carbon with high specific surface area (> 1000 m2/
G) as the main body for carrying sulphur, a certain amount of high-specific surface area carbon black materials (> 600 m are added2/ g), and a certain amount of mistake is added
Metal or transient metal sulfide are crossed, the capacity that can effectively improve lithium-sulfur cell plays and cyclical stability.Due to carbon black
High-specific surface area, carbon black not only play the effect of enhancing electric conductivity in compound system, while also as the carrier of sulphur, Ke Yibao
Higher load sulphur specific gravity is demonstrate,proved, is solved merely using active carbon as the weakness of the carbon-sulfur compound poorly conductive of carrier.Metal or
Metallic compound can play fixed function to the more lithium sulfides of electrochemistry intermediate product, show than simple carbon material strongerization
Absorption is learned, the shuttle effect of more sulphions is inhibited, the capacity for effectively improving lithium-sulfur cell plays 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.
Carbon black alternatively some significant differences existing for Carbon Materials and active carbon.Firstly, raw material is different, it is living
The raw material of property charcoal is coke or natural organic plant etc, and the raw material of carbon black is these petroleum products such as heavy oil coal tar.Its
Secondary, structure is different, and active carbon particle is bigger, is micron order, and specific surface area is relatively high；The particle of carbon black is thinner, is to receive
Meter level, chain structure, specific surface area size can regulate and control.Third is that the two electric conductivity is different, the electric conductivity of active carbon is not so good as charcoal
It is black.The good electric conductivity of carbon black can be used for improving the electric conductivity of lithium sulfur battery anode material, improve specific capacity and cycle performance.
In addition, carbon black materials can have higher specific surface area, therefore it on the one hand can improve the electric conductivity of positive electrode, another party
Face can also be used as the carrier of sulphur, improve the load sulfur content of anode.
Specific embodiment 1: present embodiment record is a kind of lithium sulfur battery anode material, the positive electrode
Comprising active carbon, carbon black, transition metal and sulphur, active carbon, carbon black, transition metal and sulphur mass ratio be 10 ~ 30:1 ~ 10:1 ~
10:60 ~ 80.
Specific embodiment 2: a kind of lithium sulfur battery anode material described in specific embodiment one, the active carbon
1000 ~ 4000 m of specific surface area2/g；600 ~ 3000 m of specific surface area of the carbon black2/g；The transition metal is 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 distillation
Sulphur.
Specific embodiment 3: a kind of preparation of lithium sulfur battery anode material described in a kind of specific embodiment one or two
Method, it is described the preparation method is as follows: active carbon, carbon black and transition metal are mixed, grinding, until mixture being capable of whole mistakes
Sieve, then mixed with sulphur, grinding enables mixture to be all sieved, and adds carbon disulfide to flood the surface of solids, is stored at room temperature
Until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated, 60 ~ 100oC forced air drying 6 ~ for 24 hours, it grinds and is sieved, 150 ~
350oC is placed on 1 ~ 24 h of heating in closed container, grinds and is sieved to get lithium sulfur battery anode material is arrived；The mesh of sieve used
Number is 50 ~ 300 mesh；Described is ground to hand lapping or mechanical ball mill.
Specific embodiment 4: a kind of lithium sulphur electricity of lithium sulfur battery anode material prepared containing specific embodiment three
Pond, the lithium-sulfur cell are the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: it is described just
Pole piece the preparation method comprises the following steps: by positive electrode, conductive agent, binder according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio be dispersed in from
Form slurry in sub- water, the solid content of slurry is 20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heating 3
~ 48 h drying, wherein surface density of the slurry on utter misery aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium gold
Category or lithium alloy；The diaphragm is the polyolefin micropore of (1) polyolefin micropore barrier diaphragm substrate, (2) surface coated with polymer
Barrier film base material, (3) surface polyolefin micropore barrier diaphragm substrate or (4) surface coated with ceramics are coated with polymer and ceramic and gather
Alkene micro-pore septum substrate；The electrolyte is ethers electrolyte.
Specific embodiment 5: a kind of lithium sulphur electricity of lithium sulfur battery anode material containing specific embodiment one or two
Pond, the lithium-sulfur cell are the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: it is described just
Pole piece the preparation method comprises the following steps: by positive electrode, conductive agent, binder according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio be dispersed in from
Form slurry in sub- water, the solid content of slurry is 20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heating 3
~ 48 h drying, wherein surface density of the slurry on utter misery aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium gold
Category or lithium alloy；The diaphragm is the polyolefin micropore of (1) polyolefin micropore barrier diaphragm substrate, (2) surface coated with polymer
Barrier film base material, (3) surface polyolefin micropore barrier diaphragm substrate or (4) surface coated with ceramics are coated with polymer and ceramic and gather
Alkene micro-pore septum substrate；The electrolyte is ethers electrolyte.
Specific embodiment 6: present embodiment record is a kind of lithium sulfur battery anode material, the positive electrode
Comprising active carbon, carbon black, transistion metal compound and sulphur, active carbon, carbon black, transistion metal compound and sulphur mass ratio be 10
~ 30:1 ~ 10:1 ~ 10:60 ~ 80.
Specific embodiment 7: a kind of lithium sulfur battery anode material described in specific embodiment six, the active carbon
1000 ~ 4000 m of specific surface area2/g；600 ~ 3000 m of specific surface area of the carbon black2/g；The transition metal compound
Object is transition metal carbide, transition metal boride, transition metal nitride, transition metal phosphide, transiting metal oxidation
One of object and transient metal sulfide are a variety of；The sulphur is sublimed sulfur.
Specific embodiment 8: a kind of lithium sulfur battery anode material described in specific embodiment seven, the transition gold
Category 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,
One of Ti-B, Cr-B, Zr-B or a variety of；The transition metal nitride is WN, VN, TiN, W2N, LaN, Mo2In N
It is one or more；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 9: a kind of lithium sulphur described in any specific embodiment in a kind of specific embodiment six to eight
The preparation method of cell positive material, it is described the preparation method is as follows: by active carbon, carbon black and transistion metal compound mix,
Grinding until mixture can all be sieved, then is mixed with sulphur, and grinding enables mixture to be all sieved, and adds curing
Carbon flooded the surface of solids, was stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated, 60 ~ 100oC air blast is dry
Dry 6 ~ for 24 hours, and it grinds and is sieved, 150 ~ 350oC is placed on 1 ~ 24 h of heating in closed container, grinds and is sieved to get lithium sulphur is arrived
Cell positive material；The mesh number of sieve used is 50 ~ 300 mesh；Described is ground to hand lapping or mechanical ball mill.
Specific embodiment 10: a kind of lithium sulphur electricity of lithium sulfur battery anode material prepared containing specific embodiment nine
Pond, the lithium-sulfur cell are the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: it is described just
Pole piece the preparation method comprises the following steps: by positive electrode, conductive agent, binder according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio be dispersed in from
Form slurry in sub- water, the solid content of slurry is 20% ~ 50%, slurry is coated on utter misery aluminium foil, then 60 ~ 100oC heating 3
~ 48 h drying, wherein surface density of the slurry on utter misery aluminium foil is 1 ~ 20 mg/cm2；The negative electrode tab contains lithium gold
Category or lithium alloy；The diaphragm is the polyolefin micropore of (1) polyolefin micropore barrier diaphragm substrate, (2) surface coated with polymer
Barrier film base material, (3) surface polyolefin micropore barrier diaphragm substrate or (4) surface coated with ceramics are coated with polymer and ceramic and gather
Alkene micro-pore septum substrate；The electrolyte is ethers electrolyte.
A kind of specific embodiment 11: lithium sulphur electricity containing specific embodiment any in specific embodiment six to eight
The lithium-sulfur cell of pond positive electrode, the lithium-sulfur cell are the laminated battery for including positive plate, negative electrode tab, diaphragm and electrolyte
Pond；Specific: the positive plate is the preparation method comprises the following steps: by positive electrode, conductive agent, binder according to 80 ~ 99:0 ~ 10:1 ~ 10
Mass ratio dispersion form slurry in deionized water, the solid content of slurry is 20% ~ 50%, and slurry is coated on utter misery aluminium foil,
Then 60 ~ 100oC heats 3 ~ 48 h drying, wherein surface density of the slurry on utter misery aluminium foil is 1 ~ 20 mg/cm2；It is described
Negative electrode tab contain lithium metal or lithium alloy；The diaphragm is (1) polyolefin micropore barrier diaphragm substrate, (2) surface coated with poly-
Close the polyolefin micropore barrier diaphragm substrate of object, (3) surface is coated with the polyolefin micropore barrier diaphragm substrate of ceramics or (4) surface is coated with
The polyolefin micropore barrier diaphragm substrate of polymer and ceramics；The electrolyte is ethers electrolyte.
Embodiment 1
Active carbon (commercially available, 1000 m of specific surface area2/ g), carbon black (commercially available, 600 m of specific surface area2/ g) and VS2(commercially available) is with matter
Amount is mixed than 2:1:1, and grinding is crossed 80 meshes, then mixed with sublimed sulfur, grinds, carbon disulfide is added to flood the surface of solids,
It stands and places until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated, dry, grinding, 200 DEG C are placed on closed container
6 h of middle heating, grinding cross 150 meshes, obtain positive electrode C1, each component mass ratio: active carbon: carbon black: VS2: sulphur 20:
10:10:60。
Comparative example 1-1
Places comparative example 1-1 different from embodiment 1 are, are added without VS2Component, by active carbon and carbon black with the ratio of 3:1
Mixing, finally obtains positive electrode C1-1, each component mass ratio: active carbon: carbon black: sulphur 30:10:60.
Comparative example 1-2
Places comparative example 1-2 different from embodiment 1 are, are added without carbon black component, by active carbon and VS2With the ratio of 3:1
Mixing, finally obtains positive electrode C1-2, each component mass ratio: active carbon: VS2: sulphur 30:10:60.
Comparative example 1-3
Places comparative example 1-3 different from embodiment 1 are, are added without carbon black and VS2Component finally obtains positive electrode C1-
3, each component mass ratio: active carbon: sulphur 40:60.
Embodiment 2
Active carbon (commercially available, 2100 m of specific surface area2/ g), carbon black (commercially available, 1700 m of specific surface area2/ g) and Co(commercially available from) with matter
Amount is mixed than 2:1:1, and grinding is crossed 200 meshes, then mixed with sublimed sulfur, grinds, carbon disulfide is added to flood solid table
Face stands and places until carbon disulfide volatilization is clean, and the sulphur that removal surface is precipitated, dry, grinding, 155 DEG C are placed on closed appearance
Heat 12 h in device, grind, cross 300 meshes, obtain positive electrode C2, each component mass ratio: active carbon: carbon black: Co: sulphur is
10:5:5:80。
Comparative example 2-1
Places comparative example 2-1 different from embodiment 2 are, are added without carbon black and Co component, obtain positive electrode C2-1, each group
Divide mass ratio: active carbon: sulphur 20:80.
Embodiment 3
Active carbon (commercially available, 1400 m of specific surface area2/ g), carbon black (commercially available, 1400 m of specific surface area2/ g) and Fe3Commercially available from C() with
Mass ratio 30:2:3 mixing, grinding sieve with 100 mesh sieve, then mixed with sublimed sulfur, grind, carbon disulfide is added to flood solid
Surface stands and places until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated, dry, grinding, 200 DEG C be placed on it is closed
24 h of vessel in heating, grinding cross 200 meshes, obtain positive electrode, each component mass ratio: active carbon: carbon black: Fe3C: sulphur is
30:2:3:65。
Comparative example 3-1
Places comparative example 3-1 different from embodiment 3 are, are added without carbon black and metal oxide component, obtain positive electrode
C3-1, each component mass ratio: active carbon: sulphur 35:65.
Embodiment 4
Active carbon (commercially available, 1400 m of specific surface area2/ g), carbon black (commercially available, 1700 m of specific surface area2/ g) and WP(commercially available from) with matter
Amount is mixed than 4:1:1, and grinding sieves with 100 mesh sieve, then mixed with sublimed sulfur, grinds, carbon disulfide is added to flood solid table
Face stands and places until carbon disulfide volatilization is clean, and the sulphur that removal surface is precipitated, dry, grinding, 350 DEG C are placed on closed appearance
48 h are heated in device, are ground, are sieved with 100 mesh sieve, obtain positive electrode, each component mass ratio: active carbon: carbon black: WP: sulphur 20:
5:5:70。
Comparative example 4-1
Places comparative example 4-1 different from embodiment 4 are, are added without carbon black and WP component, obtain positive electrode C4-1, each group
Divide mass ratio: active carbon: sulphur 30:70.
Embodiment 5
Active carbon (commercially available, 2100 m of specific surface area2/ g), carbon black (commercially available, 1700 m of specific surface area2/ g), ZrB2(commercially available), TiN
(commercially available), MnO2(commercially available) is crossed 50 meshes, then is mixed with sublimed sulfur, ground with mass ratio 10:10:3:3:4 mixing, grinding
Mill adds carbon disulfide to flood the surface of solids, stands and places until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated is done
Dry, grinding, 300 DEG C are placed in closed container and heat 6 h, grind, and cross 150 meshes, obtain positive electrode C5, each group sub-prime
Measure ratio: active carbon: carbon black: ZrB2: TiN:MnO2: sulphur 10:10:3:3:4:70.
Comparative example 5-1
Places comparative example 5-1 different from embodiment 5 are, are added without carbon black and components of metal compounds, obtain positive electrode
C5-1, each component mass ratio: active carbon: sulphur 30:70.
Positive plate preparation: by the above positive electrode and binder (SBR/CMC=1:1) and conductive agent (Super P) with
The mass ratio of 80:10:10 mixes, and using deionized water as solvent, is fabricated to slurry, is coated on utter misery aluminium foil, dries, is carried
Sulfur content is 2mg/cm2Positive plate.
Lithium-sulfur cell Integration Assembly And Checkout: by the above positive plate and cathode (metallic lithium foil) and electrolyte (0.5M LiTFSI
It is dissolved in the DOL/DME in the mixed solvent of volume ratio 1:1, additive is 0.1M 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 the present invention from the battery performance of the obtained positive electrode of each embodiment and comparative example in table 1 to be announced
Positive electrode and its synthetic method, higher gram volume and preferable cycle performance can be obtained.Carbon black in positive electrode
The poor defect of active carbon electric conductivity is effectively improved with metal sulfide component, be conducive to the performance of gram volume and is obtained more preferably
Cycle performance.
Claims (11)
1. a kind of lithium sulfur battery anode material, it is characterised in that: the positive electrode includes active carbon, carbon black, transition metal
And sulphur, active carbon, carbon black, transition metal and sulphur mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:60 ~ 80.
2. a kind of lithium sulfur battery anode material according to claim 1, it is characterised in that: the specific surface of the active carbon
1000 ~ 4000 m of product2/g；600 ~ 3000 m of specific surface area of the carbon black2/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 sublimed sulfur.
3. a kind of a kind of preparation method of lithium sulfur battery anode material of any of claims 1 or 2, it is characterised in that: described
The preparation method is as follows: active carbon, carbon black and transition metal are mixed, grinding, until mixture can all be sieved, then with sulphur into
Row mixing, grinding enable mixture to be all sieved, add carbon disulfide to flood the surface of solids, be stored at room temperature until carbon disulfide
Volatilization is clean, and the sulphur that removal surface is precipitated, forced air drying grinds and is sieved, and 150 ~ 350oC be placed in closed container heating 1 ~
24 h are ground and are sieved to get lithium sulfur battery anode material is arrived.
4. a kind of lithium-sulfur cell of the lithium sulfur battery anode material prepared containing claim 3, it is characterised in that: the lithium sulphur
Battery is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: the positive piece preparation method
Are as follows: positive electrode, conductive agent, binder are dispersed to be formed in deionized water according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio and starched
Material, slurry is coated on utter misery aluminium foil, then heating, drying；The negative electrode tab contains lithium metal or lithium alloy；
The diaphragm is (1) polyolefin micropore barrier diaphragm substrate, (2) surface polyolefin micropore barrier diaphragm substrate, (3) table coated with polymer
Face is coated with the polyolefin micropore barrier diaphragm substrate of ceramics or (4) surface is coated with polymer and ceramic polyolefin micropore barrier diaphragm base
Material；The electrolyte is ethers electrolyte.
5. a kind of lithium-sulfur cell of the lithium sulfur battery anode material containing claims 1 or 2, it is characterised in that: the lithium sulphur
Battery is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: the positive piece preparation method
Are as follows: positive electrode, conductive agent, binder are dispersed to be formed in deionized water according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio and starched
Material, slurry is coated on utter misery aluminium foil, then heating, drying；The negative electrode tab contains lithium metal or lithium alloy；
The diaphragm is (1) polyolefin micropore barrier diaphragm substrate, (2) surface polyolefin micropore barrier diaphragm substrate, (3) table coated with polymer
Face is coated with the polyolefin micropore barrier diaphragm substrate of ceramics or (4) surface is coated with polymer and ceramic polyolefin micropore barrier diaphragm base
Material；The electrolyte is ethers electrolyte.
6. a kind of lithium sulfur battery anode material, it is characterised in that: the positive electrode includes active carbon, carbon black, transition metal
Compound and sulphur, active carbon, carbon black, transistion metal compound and sulphur mass ratio be 10 ~ 30:1 ~ 10:1 ~ 10:60 ~ 80.
7. a kind of lithium sulfur battery anode material according to claim 6, it is characterised in that: the specific surface of the active carbon
1000 ~ 4000 m of product2/g；600 ~ 3000 m of specific surface area of the carbon black2/g；The transistion metal compound is transition
Metal carbides, transition metal boride, transition metal nitride, transition metal phosphide, transition metal oxide and transition
One of metal sulfide is a variety of；The sulphur is sublimed sulfur.
8. a kind of lithium sulfur battery anode material according to claim 7, it is characterised in that: the transition metal carbide
For 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-B, Cr-
One of B, Zr-B or a variety of；The transition metal nitride is WN, VN, TiN, W2N, LaN, Mo2One of N or more
Kind；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.
9. a kind of preparation method of lithium sulfur battery anode material described in any claim in a kind of claim 6 ~ 8, special
Sign is: described the preparation method is as follows: active carbon, carbon black and transistion metal compound are mixed, grinding, until mixture energy
Enough all sievings, then mixed with sulphur, grinding enables mixture to be all sieved, and add carbon disulfide to flood the surface of solids,
It being stored at room temperature until carbon disulfide volatilization is clean, the sulphur that removal surface is precipitated, forced air drying grinds and is sieved, and 150 ~ 350oC is put
1 ~ 24 h of heating in closed container is set, grinds and is sieved to get lithium sulfur battery anode material is arrived.
10. a kind of lithium-sulfur cell of the lithium sulfur battery anode material prepared containing claim 9, it is characterised in that: the lithium
Sulphur battery is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: the positive plate preparation side
Method are as follows: form positive electrode, conductive agent, binder in deionized water according to the dispersion of 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio
Slurry is coated on utter misery aluminium foil, then heating, drying by slurry；The negative electrode tab contains lithium metal or lithium closes
Gold；The diaphragm be (1) polyolefin micropore barrier diaphragm substrate, (2) surface be coated with polymer polyolefin micropore barrier diaphragm substrate,
(3) surface is coated with the polyolefin micropore barrier diaphragm substrate of ceramics or (4) surface is coated with polymer and ceramic polyolefin micropore
Barrier film base material；The electrolyte is ethers electrolyte.
11. lithium-sulfur cell of the one kind containing the lithium sulfur battery anode material of any claim in claim 6 ~ 8, feature exist
In: the lithium-sulfur cell is the laminated batteries for including positive plate, negative electrode tab, diaphragm and electrolyte；It is specific: it is described just
Pole piece the preparation method comprises the following steps: by positive electrode, conductive agent, binder according to 80 ~ 99:0 ~ 10:1 ~ 10 mass ratio be dispersed in from
Slurry is formed in sub- water, slurry is coated on utter misery aluminium foil, then heating, drying；The negative electrode tab contain lithium metal or
Person's lithium alloy；The diaphragm is the polyolefin micropore barrier diaphragm of (1) polyolefin micropore barrier diaphragm substrate, (2) surface coated with polymer
Substrate, (3) surface are coated with the polyolefin micropore barrier diaphragm substrate of ceramics or (4) surface is coated with polymer and ceramic polyolefin
Micro-pore septum substrate；The electrolyte is ethers electrolyte.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811642045.3A CN109713282B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811642045.3A CN109713282B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109713282A true CN109713282A (en) | 2019-05-03 |
| CN109713282B CN109713282B (en) | 2020-10-09 |
Family
ID=66259641
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811642045.3A Active CN109713282B (en) | 2018-12-29 | 2018-12-29 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109713282B (en) |
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323428A (en) * | 2019-07-03 | 2019-10-11 | 上海电力学院 | A kind of anode material of lithium-ion battery and preparation method thereof |
| CN111082002A (en) * | 2019-12-03 | 2020-04-28 | 珠海冠宇电池有限公司 | Composite material and preparation method and application thereof |
| CN111403698A (en) * | 2020-04-30 | 2020-07-10 | 肇庆市华师大光电产业研究院 | Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111446439A (en) * | 2020-05-20 | 2020-07-24 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN111620406A (en) * | 2020-07-15 | 2020-09-04 | 湖南第一师范学院 | Application of CuS/Co2P composite photocatalyst in organic wastewater treatment |
| CN111740109A (en) * | 2020-06-22 | 2020-10-02 | 珠海冠宇电池股份有限公司 | Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH |
| CN111740092A (en) * | 2020-07-24 | 2020-10-02 | 广州大学 | Heterostructure material and preparation method and application thereof |
| CN111900407A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| WO2022005210A1 (en) * | 2020-07-01 | 2022-01-06 | 주식회사 엘지에너지솔루션 | Positive electrode for lithium-sulfur battery and method for manufacturing same |
| CN113943016A (en) * | 2021-10-14 | 2022-01-18 | 天目湖先进储能技术研究院有限公司 | Binary transition metal sulfide material and application thereof |
| CN114420916A (en) * | 2022-01-24 | 2022-04-29 | 福州大学 | Lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
| CN115036480A (en) * | 2022-06-17 | 2022-09-09 | 湘潭大学 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
| WO2022265234A1 (en) * | 2021-06-15 | 2022-12-22 | 주식회사 엘지에너지솔루션 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same |
Citations (3)
| 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 |
-
2018
- 2018-12-29 CN CN201811642045.3A patent/CN109713282B/en active Active
Patent Citations (3)
| 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 |
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 (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110323428A (en) * | 2019-07-03 | 2019-10-11 | 上海电力学院 | A kind of anode material of lithium-ion battery and preparation method thereof |
| CN111082002A (en) * | 2019-12-03 | 2020-04-28 | 珠海冠宇电池有限公司 | Composite material and preparation method and application thereof |
| CN111403698A (en) * | 2020-04-30 | 2020-07-10 | 肇庆市华师大光电产业研究院 | Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111403698B (en) * | 2020-04-30 | 2021-11-12 | 肇庆市华师大光电产业研究院 | Novel efficient lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111446439B (en) * | 2020-05-20 | 2021-04-13 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN111446439A (en) * | 2020-05-20 | 2020-07-24 | 中南大学 | S@MxSnSy@ C composite positive electrode active material, preparation method thereof and application of active material in lithium-sulfur battery |
| CN111740109A (en) * | 2020-06-22 | 2020-10-02 | 珠海冠宇电池股份有限公司 | Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH |
| CN111740109B (en) * | 2020-06-22 | 2021-06-08 | 珠海冠宇电池股份有限公司 | Preparation method of boron and phosphorus doped graphitized carbon-nitrogen compound cathode material activated by KOH |
| WO2022005210A1 (en) * | 2020-07-01 | 2022-01-06 | 주식회사 엘지에너지솔루션 | Positive electrode for lithium-sulfur battery and method for manufacturing same |
| CN111620406A (en) * | 2020-07-15 | 2020-09-04 | 湖南第一师范学院 | Application of CuS/Co2P composite photocatalyst in organic wastewater treatment |
| CN111740092A (en) * | 2020-07-24 | 2020-10-02 | 广州大学 | Heterostructure material and preparation method and application thereof |
| CN111900407B (en) * | 2020-08-04 | 2021-12-31 | 大连理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111900407A (en) * | 2020-08-04 | 2020-11-06 | 大连理工大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| WO2022265234A1 (en) * | 2021-06-15 | 2022-12-22 | 주식회사 엘지에너지솔루션 | Positive electrode for lithium-sulfur battery and lithium-sulfur battery comprising same |
| CN113943016A (en) * | 2021-10-14 | 2022-01-18 | 天目湖先进储能技术研究院有限公司 | Binary transition metal sulfide material and application thereof |
| CN114420916A (en) * | 2022-01-24 | 2022-04-29 | 福州大学 | Lithium-sulfur battery positive electrode material and preparation method and application thereof |
| CN114420916B (en) * | 2022-01-24 | 2023-08-25 | 福州大学 | Positive electrode material of lithium-sulfur battery, and preparation method and application thereof |
| CN114921809A (en) * | 2022-04-24 | 2022-08-19 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
| CN114921809B (en) * | 2022-04-24 | 2022-12-20 | 北京科技大学 | Preparation method of foamed nickel loaded boron-doped phosphide heterojunction |
| CN115036480A (en) * | 2022-06-17 | 2022-09-09 | 湘潭大学 | Lithium-sulfur battery positive electrode material, preparation method thereof and lithium-sulfur battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109713282B (en) | 2020-10-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109713282A (en) | A kind of lithium sulfur battery anode material and preparation method thereof and lithium-sulfur cell | |
| Zhang et al. | A strongly cooperative spinel nanohybrid as an efficient bifunctional oxygen electrocatalyst for oxygen reduction reaction and oxygen evolution reaction | |
| Pei et al. | Technologies for extending zinc–air battery’s cyclelife: A review | |
| CN105206841B (en) | A kind of pyrite class additive in lithium-sulphur cell positive electrode | |
| Sengupta et al. | 3D microporous Sn-Sb-Ni alloy impregnated Ni foam as high-performance negative electrode for lithium-ion batteries | |
| CN109786748A (en) | A kind of lithium-sulphur cell positive electrode piece and preparation method thereof, lithium-sulfur cell | |
| CN109713313A (en) | A kind of lithium-sulphur cell positive electrode piece and preparation method thereof and lithium-sulfur cell | |
| CN107507978B (en) | A kind of sodium-ion battery FeS2/Fe3O4/ C negative electrode material and preparation method thereof | |
| CN110176591A (en) | A kind of preparation method of water system zinc ion secondary cell and its anode based on organic electrode materials | |
| CN104956527A (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 | |
| CN110212159A (en) | A kind of composite negative pole pole piece and preparation method thereof | |
| CN105900267A (en) | Tungsten-based material super battery and supercapacitor | |
| CN109802150B (en) | Non-noble metal bifunctional oxygen electrode catalyst, preparation method thereof, zinc-air battery anode and zinc-air battery | |
| CN105870447A (en) | Preparation method of nitrogen-doped rutile TiO2/C negative electrode material for sodium-ion battery | |
| CN104393310A (en) | Air electrode material of high-activity lithium air battery and preparation method of nano-composite catalyst material | |
| CN107887594A (en) | A kind of compound lithium-rich manganese-based anode material and preparation method for lithium ion battery | |
| CN108899522A (en) | A kind of high-volume silicon-carbon negative electrode material, preparation method and application | |
| CN108172406A (en) | One kind is with FeS2-xSexMaterial is the sodium ion capacitor of negative material | |
| CN110277554A (en) | Positive electrode and positive plate and preparation method thereof, lithium ion battery | |
| Shen et al. | Inducing rapid polysulfide transformation through enhanced interfacial electronic interaction for lithium–sulfur batteries | |
| CN109301254A (en) | A kind of lithium sulfur battery anode material, anode and its preparation and application | |
| Song et al. | Hierarchical porous CoFe2O4/CoFe2Se4 nanosheet as supercapacitor electrodes: Effect of selenium content and pore structure on electrochemical performance | |
| CN105789579A (en) | Bionic synthesizing method of lithium ion cell anode material FeO4/Fe2O3/Fe/C | |
| CN102130358B (en) | Lithium battery and preparation method thereof | |
| CN108439474A (en) | A kind of lithium battery high-performance Ni doping MnCO3The preparation method of negative material |
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 |