CN109888176A - A kind of anode of lithium-sulfur rechargeable battery - Google Patents
A kind of anode of lithium-sulfur rechargeable battery Download PDFInfo
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Abstract
The purpose of the present invention is to provide a kind of anode of lithium-sulfur rechargeable battery, the anode includes that 1~5 layer of sulfur-bearing positive electrode material layer and 1~5 layer of lithium storage materials layer containing transition metal element, the sulfur-bearing positive electrode material layer replace coating with lithium storage materials layer.The overall thickness of the anode be 50~800 microns, the sulfur-bearing positive electrode material layer with a thickness of 1~500 micron, the lithium storage materials layer with a thickness of 1~200 micron.Electrode provided by the invention can inhibit shuttle effect and have storage lithium performance, it is possible to provide portion capacity；More active site can be provided for lithium sulfide, improve the utilization rate of sulphur.
Description
Technical field
The present invention relates to lithium-sulfur rechargeable battery technical fields, more particularly to a kind of anode of lithium-sulfur rechargeable battery.
Background technique
Lithium-sulfur rechargeable battery is a kind of high specific energy electrochemical energy storage system, mainly using sulphur as positive active material, lithium metal
For cathode, using the ethers solution of lithium salts as electrolyte.The theoretical specific capacity of elemental sulfur is up to 1675mAh/g, is stratiform cobalt acid lithium
10 times of positive electrode.But the electric conductivity of sulphur is very poor, in order to make full use of the active material sulphur in electrode, need to be added a large amount of
Conductive agent.More importantly the electric discharge intermediate product of sulphur is more sulphions of high dissolubility, it is easy to diffuse to cathode and gold
Belong to lithium occur self discharge reaction (i.e. " shuttle effect "), cause active material loss and lower coulombic efficiency.The electric discharge of sulphur
The electro-chemical activity and electric conductivity of product lithium sulfide are poor, and the lithium sulfide for being deposited on nonactive site is not easy by again sharp
With.The above reason results in that lithium-sulfur rechargeable battery active material utilization is low, coulombic efficiency is low, capacity attenuation is rapid, cyclicity
It can be poor.For improve lithium-sulfur rechargeable battery performance, mainly battery structure design, positive electrode Composite, electrolysis additive,
Negative terminal surface modification etc. improves.Wherein, study it is more be positive electrode Composite, design various composition and knot
The carrier of structure is used for sulfur loaded.For example, improving its electric conductivity, and utilize its porosity using various porous carbon materials sulfur loadeds
Matter can inhibit shuttle effect with the more sulphions of absorbed portion.In addition, the oxide of transition metal, sulfide etc. are due to its polarity
It is relatively strong, can with the more sulphions of strong adsorption, preferably inhibition shuttle effect, part of material conductivity also with higher,
Improve the electric conductivity of sulphur anode.In these sulfur-bearing positive electrodes, conductive additive and more sulphion adsorbents tend to take up compared with
Big specific gravity, to reduce the specific capacity of positive entirety.With the storage active positive electrode of lithium such as lithium-containing transition metal oxide
It can also be used for adsorbing more sulphions, and portion capacity be provided.Such as to disclose a kind of lithium-sulfur cell compound just by CN105529446A
More sulphions can be strapped in positive pole zone, improve the utilization rate of sulphur by pole material and preparation method thereof, lithium storage materials.C.-S.Kim
Etc. the composite positive pole for reporting sulphur and LiFePO4 composition, the utilization rate of sulphur and the high rate performance of battery can be improved
(C.-S.Kim,et al,Electrochemistry Communications,2013,32,35-38).But sulphur and storage lithium
The electron conduction of the anode composite of material composition is poor, a large amount of conductive carbons need to be added, and the discharging product of sulphur is easy to accumulate
On the surface of lithium storage materials, electro-chemical activity is lost, therefore the cycle performance of composed battery is bad.
In the structure of battery (electrode), the materials such as porous carbon are prepared into film and are covered on sulfur-bearing anode table by many researchs
Face, or it is applied directly to sulfur-bearing positive electrode surface, form the double-deck or electrode with sulphur concentration gradient.For example, CN103972467B
A kind of lithium-sulfur cell MULTILAYER COMPOSITE anode is disclosed, by first layer graphene film layer, carbon/sulphur active material layer, the second graphite
Alkene film layer and polymeric layer are constituted, and wherein the second layer plays the role of diaphragm, are increased electronics and ion transmission, are limited more sulphions
Shuttle.CN106207088A discloses a kind of gradient multilayer sulphur anode structure, in multilayered structure the sulfur content of each layer by it is interior extremely
Outer distribution gradient, innermost layer sulfur content highest, outermost layer not sulfur-bearing provide diffusion space for sulphur, and enhance to more sulphions
Barrier effect, more sulphions are limited in electrode space as far as possible.CN108630890A disclose it is a kind of by loose porous layer,
The lithium-sulfur rechargeable battery anode structure that conducting matrix grain layer and the confinement layer for being covered in electrode surface form, the confinement layer of electrode surface
The diffusion of more sulphions can be limited, shuttle effect is inhibited.This class formation mainly utilizes the absorption property of the materials such as porous carbon, suppression
The dissolution and shuttle effect of more sulphions are made, and certain electric conductivity is provided.But additional increased adsorption layer occupies larger volume
And quality, itself does not provide capacity, inevitably reduces the specific energy and volume energy density of battery entirety.
Summary of the invention
The purpose of the present invention is to provide a kind of anodes of lithium-sulfur rechargeable battery, can inhibit shuttle effect and have storage
Lithium performance, it is possible to provide portion capacity can provide more active site for lithium sulfide, improve the utilization rate of sulphur.
The invention provides the following technical scheme:
A kind of anode of lithium-sulfur rechargeable battery, the anode include that 1~5 layer of sulfur-bearing positive electrode material layer and 1~5 layer contain transition
The lithium storage materials layer of metallic element, the sulfur-bearing positive electrode material layer replace coating with lithium storage materials layer.
The overall thickness of the anode is 50~800 microns, the sulfur-bearing positive electrode material layer with a thickness of 1~500 micron, institute
State lithium storage materials layer with a thickness of 1~200 micron.
In the present invention, the thickness of every layer of sulfur-bearing positive electrode material layer is identical or different in anode, every layer of lithium storage materials layer
Thickness is identical or different.
Preferably, just extremely 2~6 layers of structure, the overall thickness of the anode are 150~180 microns, the anode packet
1~3 layer of sulfur-bearing positive electrode material layer and 1~3 layer of lithium storage materials layer containing transition metal element of alternately coating are included, the sulfur-bearing is just
Pole material layer with a thickness of 10~60 microns, the lithium storage materials layer with a thickness of 10~50 microns.Lithium storage materials layer is inhibiting
While shuttle effect, it is that sulfur-bearing positive electrode material layer increases more active sites by multilayered structure, sulphur and sulphur can be extended
Change the electrochemical reaction region of lithium；But too in view of the overall thickness of anode and every layer of sulfur-bearing positive electrode material layer and lithium storage materials layer
It is not easy coating molding when thin, therefore above-mentioned thickness and the easily prepared molding of the number of plies and there is preferable performance.
The sulfur-bearing positive electrode material layer includes sulphur, conductive carbon and binder, the mass ratio of the sulphur, conductive carbon and binder
For 30~90:10~70:2~20.Preferably, the mass ratio of the sulphur, conductive carbon and binder be 40~80:30~50:8~
10.The electric conductivity of sulphur is poor, generally to add some conductive carbons.
When preparing sulfur-bearing positive electrode material layer, sulphur/carbon composite, including elemental sulfur and conductive carbon A are prepared first, sulphur
Content controls between 20~95%, and preferred value is 50~85%.Conductive carbon A in the sulphur/carbon composite is selected from activity
One of charcoal, graphene, carbon nanotube, acetylene black or Ketjen black or at least two combination.Preferably, it is multiple to prepare sulphur/carbon
The conductive carbon A of condensation material is selected from active carbon or Ketjen black.Sulphur/carbon composite of preparation is mixed with conductive carbon B and binder again
Sulfur-bearing positive electrode material layer is obtained, the conductive carbon B is selected from one of graphene, carbon nanotube, acetylene black.Preferably, described
Conductive carbon B is selected from acetylene black.
The lithium storage materials layer includes lithium storage materials, conductive carbon and binder, mass ratio be 60~90:10~30:1~
15.Preferably, the mass ratio of the lithium storage materials, conductive carbon and binder is 70~90:15~20:2~8.Lithium storage materials account for
It is higher to account for the more more then energy contents of battery of mass fraction because it provides energy according to most of quality.Conductive carbon plays electric action, bonding
Agent guarantees that electrode can form a film.
In the present invention, the composition of every layer of sulfur-bearing positive electrode material layer and its mass ratio are identical or different, every layer of lithium storage materials
The composition and its mass ratio of layer are identical or different.
Binder in the sulfur-bearing positive electrode material layer and lithium storage materials layer is selected from oiliness binder or aqueous binders, institute
It states binder and is selected from Kynoar, nitrile rubber, carboxymethyl cellulose, butadiene-styrene rubber or acrylonitrile multiple copolymer；It is described
Binder in sulfur-bearing positive electrode material layer is opposite with the polarity of binder in lithium storage materials layer.
Conductive carbon in the sulfur-bearing positive electrode material layer and lithium storage materials layer is in graphene, carbon nanotube, acetylene black
One kind.Preferably, the conductive carbon in the sulfur-bearing positive electrode material layer and lithium storage materials layer is selected from acetylene black.
The lithium storage materials are selected from LiFePO4, ferrous disulfide, ferrous sulfide, lithium vanadate, vanadic anhydride, vanadium phosphate
One of lithium, cobalt acid lithium, lithium nickelate, LiMn2O4, nickel manganese cobalt acid lithium, lithium titanate or at least two combination.Preferably, described
Lithium storage materials are a kind of in ferrous disulfide, ferrous sulfide, lithium vanadate, LiMn2O4, vanadic anhydride or lithium titanate or at least
Two kinds of combination.To match with the voltage range of sulphur anode, and consider the adsorption capacity to more lithium sulfides, preferably above-mentioned storage lithium
Material.
Preferably, the anode includes that 2~3 layers of sulfur-bearing positive electrode material layer alternately coated and 2~3 layers contain transition metal member
The lithium storage materials layer of element, the overall thickness of the anode are 150~180 microns, the positive electrode material layer it is micro- with a thickness of 20~50
Rice, the lithium storage materials layer with a thickness of 20~50 microns, lithium storage materials in the lithium storage materials layer are selected from LiMn2O4 or five
V 2 O, the mass ratio of the lithium storage materials, conductive carbon and binder are 80~85:10~15:5.In view of battery process
Compatibility, too thin electrode is not easy coating molding；And the specific choice of lithium storage materials, the lithium of above-mentioned processing range preparation
The better performances of the anode of sulphur battery.
It is further preferred that just extremely 4 layers of structure, sequentially consist of sulfur-bearing positive electrode material layer, lithium storage materials
Layer, sulfur-bearing positive electrode material layer and lithium storage materials layer, thickness are respectively 50 microns, 20 microns, 50 microns and 30 microns；The sulfur-bearing
The mass ratio of sulphur and active carbon is 50:50, sulphur/carbon composite and acetylene black and fourth in sulphur/carbon composite in positive electrode
The mass ratio of benzene rubber is 70:20:10；The mass ratio of LiMn2O4 and acetylene black and Kynoar is in the lithium storage materials layer
80:15:5.
In the present invention, the thickness of lithium storage materials layer is accordingly set according to the thickness of sulfur-bearing positive electrode material layer, makes to store up lithium material
The bed of material has enough suction-operateds to sulfur-bearing positive electrode material layer and provides more active site, and lithium storage materials layer can rise
To the effect of support sulfur-bearing positive electrode material layer.
The beneficial effects of the present invention are design the positive electrode of multilayered structure, by the storage lithium material containing transition metal element
The bed of material is placed in the outside of sulfur-bearing positive electrode material layer, has the function of three aspects: first is that there are stronger more sulphion suction-operateds,
It can inhibit shuttle effect；Second is that itself having storage lithium performance, it is possible to provide portion capacity；Third is that can be provided for lithium sulfide more
Active site, expand sulphur and lithium sulfide electrochemical reaction region, improve the utilization rate of active material.Lithium provided by the invention
Sulfur rechargeable battery anode structure is simple, compatible with existing lithium ion battery coating processes, is produced on a large scale.
Detailed description of the invention
Fig. 1 is the anode structure schematic diagram of lithium-sulfur rechargeable battery provided by the invention；
Fig. 2 is the cyclic voltammetry curve of the anode of lithium-sulfur rechargeable battery in embodiment 1；
Fig. 3 is the cycle performance of the anode of lithium-sulfur rechargeable battery in embodiment 1；
Fig. 4 is the cyclic voltammetry curve of the anode of lithium-sulfur rechargeable battery in embodiment 4；
Fig. 5 is the cycle performance of the anode of lithium-sulfur rechargeable battery in embodiment 4；
Fig. 6 is the cycle performance of the anode of lithium-sulfur rechargeable battery in comparative example 1.
Specific embodiment
Below in conjunction with examples and drawings, the present invention is further illustrated.
Embodiment 1
(1) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 70:30, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.By resulting sulphur/carbon composite and acetylene black and carboxymethyl cellulose with
The ratio of 70:20:10 mixes, and suitable quantity of water is added, slurry is made, and is coated on aluminium foil fluid, true at 100 DEG C after natural drying
Sky is dry for 24 hours, sulfur-bearing positive electrode material layer is obtained, with a thickness of 100 microns.
(2) appropriate N- methyl is added with the ratio ground and mixed of 85:10:5 in lithium vanadate and acetylene black and Kynoar
Slurry is made as solvent in pyrrolidones, is coated on sulfur-bearing positive electrode material layer, is dried in vacuo at 100 DEG C after natural drying
For 24 hours, with a thickness of 50 microns.
Obtained double-layer structure lithium-sulfur rechargeable battery anode, overall thickness are 150 microns.The battery performance assembled such as Fig. 2
Shown in 3, the capacity retention ratio after charge and discharge 100 are enclosed between 1.0~3.5V is 75%.
Embodiment 2
(1) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 70:30, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.By resulting sulphur/carbon composite and acetylene black and carboxymethyl cellulose with
The ratio of 70:20:10 mixes, and suitable quantity of water is added, slurry is made, and is coated on aluminium foil fluid, true at 100 DEG C after natural drying
Sky is dry for 24 hours, sulfur-bearing positive electrode material layer is obtained, with a thickness of 60 microns.
(2) appropriate N- is added with the ratio ground and mixed of 80:15:5 in ferrous disulfide and acetylene black and Kynoar
Slurry is made as solvent in methyl pyrrolidone, is coated on sulfur-bearing positive electrode material layer, after natural drying the vacuum at 100 DEG C
It dries for 24 hours, with a thickness of 20 microns.
(3) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 60:40, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.By resulting sulphur/carbon composite and acetylene black and carboxymethyl cellulose with
The ratio of 70:20:10 mixes, and suitable quantity of water is added, slurry is made, and is coated on step (2) resulting electrode, exists after natural drying
It is dried in vacuo at 100 DEG C for 24 hours, coated sulfur-bearing positive electrode material layer, with a thickness of 50 microns.
(4) appropriate N- is added with the ratio ground and mixed of 80:15:5 in ferrous disulfide and acetylene black and Kynoar
Slurry is made as solvent in methyl pyrrolidone, is coated on sulfur-bearing positive electrode material layer, after natural drying the vacuum at 100 DEG C
It dries for 24 hours, with a thickness of 20 microns.
As shown in Figure 1 (1 be aluminium foil fluid, 2 be sulfur-bearing positive electrode material layer, 3 be lithium storage materials layer), gained four-layer structure
Lithium-sulfur rechargeable battery anode, overall thickness are 150 microns.Appearance of the composed battery between 1.5~3.5V after the circle of charge and discharge 100
Measuring conservation rate is 75%.
Embodiment 3
(1) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 50:50, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.Resulting sulphur/carbon composite is mixed with acetylene black and SBR emulsion
The mass ratio that slurry, sulphur/carbon composite and acetylene black and butadiene-styrene rubber is made is 70:20:10, is coated on aluminium foil fluid,
It is dried in vacuo at 100 DEG C for 24 hours after natural drying, obtains sulfur-bearing positive electrode material layer, with a thickness of 100 microns.
(2) appropriate N- first is added with the ratio ground and mixed of 80:15:5 in LiFePO4 and acetylene black and Kynoar
Slurry is made as solvent in base pyrrolidones, is coated on sulfur-bearing positive electrode material layer, and vacuum is dry at 100 DEG C after natural drying
It is dry for 24 hours, with a thickness of 50 microns.
The lithium-sulfur rechargeable battery anode of gained double-layer structure, overall thickness are 150 microns.The battery assembled 1.5~
Capacity retention ratio after charge and discharge 100 are enclosed between 3.5V is 70%.
Lithium storage materials are different to the absorption property of more sulphions, and lithium storage materials are different from the charge and discharge platform of sulphur, store up lithium material
The charge and discharge platform current potential of material is generally higher than sulphur, and the cycle performance of lithium storage materials itself is also different.Therefore with embodiment 1 or implement
It is compared in example 2 using lithium vanadate or ferrous disulfide as lithium storage materials, performance is declined.
Embodiment 4
(1) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 50:50, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.Resulting sulphur/carbon composite is mixed with acetylene black and SBR emulsion
The mass ratio that slurry, sulphur/carbon composite and acetylene black and butadiene-styrene rubber is made is 70:20:10, is coated on aluminium foil fluid,
It is dried in vacuo at 100 DEG C for 24 hours after natural drying, obtains sulfur-bearing positive electrode material layer, with a thickness of 50 microns.
(2) appropriate N- methyl is added with the ratio ground and mixed of 80:15:5 in LiMn2O4 and acetylene black and Kynoar
Slurry is made as solvent in pyrrolidones, is coated on sulfur-bearing positive electrode material layer, is dried in vacuo at 100 DEG C after natural drying
For 24 hours, with a thickness of 20 microns.
(3) gained slurry in step (1) is coated on the electrode surface of step (2), it is true at 100 DEG C after natural drying
Sky is dry for 24 hours, sulfur-bearing positive electrode material layer is obtained, with a thickness of 50 microns.
(4) coating obtained by step (2) is coated on sulfur-bearing positive electrode material layer, vacuum is dry at 100 DEG C after natural drying
It is dry for 24 hours, with a thickness of 30 microns.
The lithium-sulfur rechargeable battery anode of gained four-layer structure, overall thickness are 150 microns.The battery performance assembled such as attached drawing
Shown in 4 and 5, the capacity retention ratio after charge and discharge 100 are enclosed between 1.5~3.5V is 90%.
Embodiment 5
(1) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 80:20, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.Resulting sulphur/carbon composite is mixed with acetylene black and SBR emulsion
The mass ratio that slurry, sulphur/carbon composite and acetylene black and butadiene-styrene rubber is made is 70:20:10, is coated on aluminium foil fluid,
It is dried in vacuo at 100 DEG C for 24 hours after natural drying, obtains sulfur-bearing positive electrode material layer, with a thickness of 50 microns.
(2) appropriate N- is added with the ratio ground and mixed of 80:15:5 in vanadic anhydride and acetylene black and Kynoar
Slurry is made as solvent in methyl pyrrolidone, is coated on sulfur-bearing positive electrode material layer, after natural drying the vacuum at 100 DEG C
It dries for 24 hours, with a thickness of 20 microns.
(3) gained slurry in step (1) is coated on the electrode surface of step (2), it is true at 100 DEG C after natural drying
Sky is dry for 24 hours, sulfur-bearing positive electrode material layer is obtained, with a thickness of 20 microns.
(4) slurry obtained by step (2) is coated on sulfur-bearing positive electrode material layer, vacuum is dry at 100 DEG C after natural drying
It is dry for 24 hours, with a thickness of 20 microns.
(5) after by mass ratio for the elemental sulfur and active carbon ground and mixed of 50:50, being heated to 165 DEG C makes sulphur melt and seep
Enter and obtains sulphur/carbon composite into active carbon.Resulting sulphur/carbon composite is mixed with acetylene black and SBR emulsion
The mass ratio that slurry, sulphur/carbon composite and acetylene black and butadiene-styrene rubber is made is 70:20:10, is coated on aluminium foil fluid,
It is dried in vacuo at 100 DEG C for 24 hours after natural drying, obtains sulfur-bearing positive electrode material layer, with a thickness of 20 microns.
(6) appropriate N- is added with the ratio ground and mixed of 80:15:5 in vanadic anhydride and acetylene black and Kynoar
Slurry is made as solvent in methyl pyrrolidone, is coated on sulfur-bearing positive electrode material layer, after natural drying the vacuum at 100 DEG C
It dries for 24 hours, with a thickness of 50 microns.
The lithium-sulfur rechargeable battery anode of gained six layer structure, overall thickness are 180 microns.Composed battery 1.5~
Capacity retention ratio after charge and discharge 100 are enclosed between 3.0V is 80%.
Comparative example 1
(1) after the elemental sulfur, active carbon, LiMn2O4 ground and mixed for being 50:50:20 by mass ratio, being heated to 165 DEG C makes sulphur
Melt and penetrate into and obtains sulphur/carbon/LiMn2O4 composite material in active carbon and LiMn2O4.
(2) resulting sulphur/carbon/LiMn2O4 composite material and acetylene black and Kynoar are ground with the ratio of 70:20:10
Mill mixing, is added appropriate N-Methyl pyrrolidone as solvent, slurry is made, and is coated in aluminum foil current collector, after natural drying
It is dried in vacuo at 100 DEG C for 24 hours, with a thickness of 150 microns, obtains not stratified lithium-sulfur rechargeable battery anode.The battery assembled
The cycle performance of charge and discharge is as shown in Fig. 6 between 1.5~3.5V, and capacity retention ratio is 55% after 100 circle of circulation.
Claims (8)
1. a kind of anode of lithium-sulfur rechargeable battery, which is characterized in that the anode include 1~5 layer of sulfur-bearing positive electrode material layer and 1~
5 layers of lithium storage materials layer containing transition metal element, the sulfur-bearing positive electrode material layer replace coating with lithium storage materials layer.
2. the anode of lithium-sulfur rechargeable battery according to claim 1, which is characterized in that the overall thickness of the anode be 50~
800 microns, the sulfur-bearing positive electrode material layer with a thickness of 1~500 micron, the lithium storage materials layer it is micro- with a thickness of 1~200
Rice.
3. the anode of lithium-sulfur rechargeable battery according to claim 2, which is characterized in that the overall thickness of the anode is 150
~180 microns, the anode is including alternately 1~3 layer of sulfur-bearing positive electrode material layer of coating and 1~3 layer containing transition metal element
Lithium storage materials layer, the sulfur-bearing positive electrode material layer with a thickness of 10~60 microns, the lithium storage materials layer with a thickness of 10~50
Micron.
4. the anode of lithium-sulfur rechargeable battery according to claim 1, which is characterized in that the sulfur-bearing positive electrode material layer includes
Elemental sulfur, conductive carbon and binder, mass ratio are 30~90:10~70:2~20.
5. the anode for the lithium-sulfur rechargeable battery stated according to claim 1, which is characterized in that the lithium storage materials layer includes storage lithium material
Material, conductive carbon and binder, mass ratio are 60~90:10~30:1~15.
6. the anode of lithium-sulfur rechargeable battery according to claim 4 or 5, which is characterized in that the binder is selected from oiliness
Binder or aqueous binders, the binder be selected from Kynoar, nitrile rubber, carboxymethyl cellulose, butadiene-styrene rubber or
Acrylonitrile multiple copolymer；The polarity phase of binder and the binder in lithium storage materials layer in the sulfur-bearing positive electrode material layer
Instead.
7. the anode of lithium-sulfur rechargeable battery according to claim 1, which is characterized in that the lithium storage materials are selected from ferric phosphate
Lithium, ferrous disulfide, ferrous sulfide, lithium vanadate, vanadic anhydride, phosphoric acid vanadium lithium, cobalt acid lithium, lithium nickelate, LiMn2O4, nickel manganese cobalt
One of sour lithium, lithium titanate or at least two combination.
8. the anode of lithium-sulfur rechargeable battery according to claim 7, which is characterized in that the anode includes alternately coating 2
~3 layers of sulfur-bearing positive electrode material layer and 2~3 layers of lithium storage materials layer containing transition metal element, the overall thickness of the anode is 150~
180 microns, the positive electrode material layer with a thickness of 20~50 microns, the lithium storage materials layer with a thickness of 20~50 microns, institute
It states lithium storage materials in lithium storage materials layer and is selected from LiMn2O4 or vanadic anhydride, the lithium storage materials, conductive carbon and binder
Mass ratio is 80~85:10~15:5.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113506953A (en) * | 2021-06-02 | 2021-10-15 | 郑州轻工业大学 | Application of lithium vanadium phosphate in coating of lithium-sulfur battery diaphragm |
| CN114023919A (en) * | 2021-10-20 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | High-capacity sulfur positive electrode and lithium-sulfur battery containing same |
| CN114079038A (en) * | 2020-08-12 | 2022-02-22 | 清华大学 | High-sulfur-capacity lithium-sulfur battery positive electrode and preparation method thereof |
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| CN101346835A (en) * | 2005-12-27 | 2009-01-14 | 松下电器产业株式会社 | Electrode for lithium secondary battery and lithium secondary battery using same |
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| CN103972467A (en) * | 2013-02-06 | 2014-08-06 | 中国科学院金属研究所 | Lithium-sulfur battery multilayer composite positive electrode and preparation method thereof |
| CN106463682A (en) * | 2014-04-30 | 2017-02-22 | 罗伯特·博世有限公司 | Protective layer system for a metallic lithium anode |
| CN105529446A (en) * | 2016-01-20 | 2016-04-27 | 中南大学 | Lithium-sulfur battery composite positive electrode material and preparation method and application therefor |
| CN107579201A (en) * | 2017-09-14 | 2018-01-12 | 珠海格力电器股份有限公司 | Multilayer body and preparation method thereof |
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| CN114079038B (en) * | 2020-08-12 | 2023-09-26 | 清华大学 | High-sulfur-load lithium-sulfur battery positive electrode and preparation method thereof |
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| CN114023919A (en) * | 2021-10-20 | 2022-02-08 | 中国科学院上海硅酸盐研究所 | High-capacity sulfur positive electrode and lithium-sulfur battery containing same |
| CN114023919B (en) * | 2021-10-20 | 2023-08-08 | 中国科学院上海硅酸盐研究所 | High-load sulfur positive electrode and lithium sulfur battery containing high-load sulfur positive electrode |
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