CN103138002B - Lithium-sulfur cell and preparation method thereof - Google Patents
Lithium-sulfur cell and preparation method thereof Download PDFInfo
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- CN103138002B CN103138002B CN201310071234.0A CN201310071234A CN103138002B CN 103138002 B CN103138002 B CN 103138002B CN 201310071234 A CN201310071234 A CN 201310071234A CN 103138002 B CN103138002 B CN 103138002B
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- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000003792 electrolyte Substances 0.000 claims abstract description 40
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 39
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 35
- 239000002904 solvent Substances 0.000 claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims description 15
- 239000000956 alloy Substances 0.000 claims description 15
- 238000004070 electrodeposition Methods 0.000 claims description 11
- 239000000758 substrate Substances 0.000 claims description 7
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000000151 deposition Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 4
- 239000006256 anode slurry Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 239000004020 conductor Substances 0.000 claims description 4
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 3
- 239000011530 conductive current collector Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 29
- 239000011593 sulfur Substances 0.000 abstract description 29
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 7
- 239000011149 active material Substances 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000005864 Sulphur Substances 0.000 abstract 5
- 239000000243 solution Substances 0.000 description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 8
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000013543 active substance Substances 0.000 description 6
- 229910000733 Li alloy Inorganic materials 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000001989 lithium alloy Substances 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 229910052745 lead Inorganic materials 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005459 micromachining Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052714 tellurium Inorganic materials 0.000 description 2
- 229910052718 tin Inorganic materials 0.000 description 2
- -1 trifluoromethanesulfonic acid imide Chemical class 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002772 conduction electron Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- JJQZDUKDJDQPMQ-UHFFFAOYSA-N dimethoxy(dimethyl)silane Chemical compound CO[Si](C)(C)OC JJQZDUKDJDQPMQ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of lithium-sulfur cell and preparation method thereof.This lithium-sulfur cell comprises positive pole, electrolyte and contains cathode of lithium, and described electrolyte comprises solvent and electrolyte, and wherein, described positive pole preferably adopts the porous electrode of not sulfur-bearing, and also containing sulphur and/or sulfide in described electrolyte, described electrolyte comprises lithium salts; Its preparation method comprises: prepare positive pole, electrolyte respectively and contain cathode of lithium, and this three is assembled formation target product.The invention provides a kind of simple lithium-sulfur cell system, avoid the complicated preparation process of sulphur positive pole, decrease process costs, and the skewness of active material sulphur in traditional sulphur positive electrode or the oversize capacity caused can be avoided to be difficult to play, the problems such as the utilance of sulphur is low, and battery performance is unstable.
Description
Technical Field
The invention relates to a lithium battery, in particular to a lithium-sulfur battery and a preparation method thereof.
Technical Field
The lithium-sulfur battery is paid attention to by research personnel due to incomparable high specific capacity and energy density, low price of materials, large storage capacity and other advantages, and particularly, the research on the lithium-sulfur battery at home and abroad is very active in recent years, and the technical breakthrough reaches the stage of practical application. In the conventional Li/S battery, active substance sulfur or sulfide is fixed on a positive electrode, and Li is generated by supposing that the sulfur of the positive electrode is completely reacted2S, the released theoretical specific capacity is 1672mAh/g, the theoretical specific energy is 2600Wh/Kg, which is higher than that of the prior commercial positive electrode materials such as metal oxide and the likeThe performance of one order of magnitude can be called as the most potential new generation lithium ion battery, and the lithium ion battery can provide energy for high-energy-consumption devices such as electric vehicles, hybrid electric vehicles, aerospace and the like, and can also be used as a cheap and efficient energy storage battery. In the scientific research field, main forces are focused on research of the anode, and diversified sulfur-containing anode materials are prepared, such as nano-sized sulfur, a carbon-sulfur compound, a sulfur-containing conductive polymer and the like, so that the utilization rate of sulfur is improved, an intermediate product, namely a polysulfide anion, is prevented from being dissolved in electrolyte, and the charging and discharging efficiency is improved. In the battery industry, some enterprises at home and abroad have developed and put into production and application lithium-sulfur batteries with high energy density. Recently, international calls for improvement of the performance of lithium-sulfur batteries cannot be limited to positive and negative electrode materials, and the innovation of the design and construction of the whole battery system should be focused, such as designing the battery structure by using a conductive carbon film as an intercalation method, improving the cycle performance of the lithium-sulfur battery, and improving the charging and discharging efficiency. However, the foregoing technologies have been around the synthesis of sulfur-containing composite positive electrodes, and the complex synthesis method, expensive raw materials and advanced technologies are used to obtain better performance, but the cycle performance is still insufficient due to the fact that the loss of active materials cannot be completely avoided.
Disclosure of Invention
Aiming at the defects of the prior art, the invention mainly aims to provide a lithium-sulfur battery which has the characteristics of simple structure, low cost, simple and convenient process and the like and also has better capacity exertion performance.
Another object of the present invention is to provide a method of manufacturing the aforementioned lithium-sulfur battery.
In order to realize the technical purpose, the invention adopts the following technical scheme:
a lithium-sulfur battery comprises a positive electrode, an electrolyte and a lithium-containing negative electrode, wherein the electrolyte comprises a solvent and an electrolyte, the electrolyte also contains sulfur and/or sulfide, and the electrolyte comprises a lithium salt.
Further, the lithium-containing negative electrode contains metallic lithium or a lithium alloy containing lithium In combination with any one or two or more of H, Na, K, Be, Mg, Ca, Ag, B, Al, Ga, In, C, Si, Ge, Sn, Zn, Pb, N, P, Sb, Bi, Se, and Te.
The concentration of the sulfur element contained in the electrolyte is preferably 0.05 to 10 mol/L.
The total concentration of lithium salts contained in the electrolyte is preferably 0.5 to 10 mol/L.
As a more preferred embodiment, the electrolyte further contains a negative electrode protection additive for protecting the lithium-containing negative electrode, and the negative electrode protection additive can be selected from, but not limited to, nitrate, alkoxysilane, and the like.
The solvent includes at least a first solvent for dissolving lithium salt and a second solvent for improving the solubility of elemental sulfur and/or sulfide, the first solvent includes an ether solvent, the ether solvent can be selected from but not limited to 1, 3-dioxolane or diethylene glycol dimethyl ether, and the like, and the second solvent can be selected from but not limited to carbon disulfide, benzene or derivatives thereof, toluene and tetrahydrofuran or derivatives thereof, and the like.
In a more preferred embodiment, the ratio of the total volume of the first solvent to the total volume of the second solvent in the solvent is 0.95 to 0.50: 1.
as one of more preferable embodiments, the positive electrode includes a porous electrode including a current collector and a conductive powder mixed with a binder coated on the current collector;
alternatively, the porous electrode comprises a porous conductive structure formed by electrodeposition or micromachining methods.
As one of the more preferred embodiments, the lithium-containing negative electrode comprises a lithium or lithium alloy electrode.
As one of more preferred embodiments, the method for preparing the lithium-sulfur battery may include:
(1) providing a positive electrode comprising:
a. mixing a porous conductive material, a binder and a solvent to form anode slurry, coating the anode slurry on a current collector, and drying to form an anode; or,
b. depositing an alloy layer on the substrate by taking an electro-deposition or chemical deposition solution, and then etching to remove more than one selected alloy component and/or substrate substance in the alloy layer to form the anode with a porous structure;
(2) providing a lithium-containing anode comprising:
a. depositing an electro-deposition solution on a conductive current collector to form a lithium or lithium-containing alloy interface layer; or,
b. directly cutting lithium or lithium-containing alloy into a required shape and compounding the required shape with a battery leading-out electrode;
(3) providing an electrolyte comprising:
dissolving a sublimed sulfur simple substance in carbon disulfide, wherein the dissolving is saturated;
dissolving a negative electrode protection additive into a mixed solvent mainly formed by 1, 3-dioxolane and diethylene glycol dimethyl ether in a volume ratio of 1:1, wherein the mixed solvent contains 1M lithium salt;
taking the mixture obtained in the step i and the mixture obtained in the step ii according to the ratio of 2: 8-3: 7, and obtaining electrolyte for later use;
(4) and combining the positive electrode, the lithium-containing negative electrode and the electrolyte to form the lithium-sulfur battery.
Compared with the prior art, the invention has the advantages that: the active substance sulfur or sulfide is dissolved in the electrolyte, so that the anode only serves as a conductive electrode, the complex preparation process of the traditional sulfur anode material is omitted, the process is simple and easy to implement, the requirement on equipment is low, the cost is low, and the problems that the capacity is difficult to exert, the utilization rate of sulfur is low, the battery performance is unstable and the like caused by uneven distribution or overlarge size of the active substance sulfur in the traditional sulfur anode material can be solved.
Detailed Description
As described above, in view of the disadvantages of the prior art, an aspect of the present invention is directed to provide a lithium-sulfur battery in which an active material sulfur is dissolved in an electrolyte, unlike a conventional lithium-sulfur battery employing a sulfur positive electrode structure.
Furthermore, the lithium-sulfur battery mainly comprises a metal lithium or lithium alloy as a negative electrode, a conductive porous electrode as a positive electrode and an electrolyte solution for dissolving lithium salt and an active substance sulfur simple substance or sulfide.
It is apparent that the present invention provides a simple lithium-sulfur battery system that avoids the complicated preparation process of the conventional sulfur positive electrode and reduces the process cost.
In a preferred embodiment, the positive electrode is preferably a conductive porous electrode, the porous electrode may be formed by coating conductive powder on a current collector, or may be a porous structure formed by electrodeposition or micromachining, and the conductive electrode may be a commonly used carbon conductive material (e.g., conductive carbon black, carbon tube, acetylene black, etc.) or an inert metal, etc.
Obviously, the positive electrode may be an electrode containing sulfur or no sulfur, and preferably an electrode containing no sulfur.
The negative electrode may be metallic lithium or a lithium alloy containing one or more of the following metals: h, Na, K, Be, Mg, Ca, Ag, B, Al, Ga, In, C, Si, Ge, Sn, Zn, Pb, N, P, Sb, Bi, Se, Te.
As a preferred embodiment, the active material dissolved in the electrolyte can be sulfur or sulfide, and the electrolyte also contains more than one lithium salt, such as commonly used twoLithium (trifluoromethanesulfonic acid imide) (LiTFSI), lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiCl)4) Etc. to ensure that the electrolyte has the conductivity requirement (greater than or equal to 10) of the common lithium ion battery-3S/cm)。
Preferably, the concentration of the lithium salt in the electrolyte is 0.5 to 10 mol/L.
Further, an additive capable of protecting the metallic lithium negative electrode, such as lithium nitrate, dimethyldimethoxysilane, tetramethoxysilane, etc., may be added to the electrolyte solution to form a solid electrolyte interface protective film on the surface of the negative electrode lithium, thereby preventing side reactions between the active material dissolved in the electrolyte solution and the lithium negative electrode.
The solvent of the electrolyte is mainly an ether solvent such as 1, 3-Dioxolane (DOL) or diethylene glycol dimethyl ether (DME), and the solvent can dissolve lithium salt.
Meanwhile, the electrolyte should also contain a solvent capable of greatly dissolving sublimed sulfur or sulfide, such as carbon disulfide, and the mass fraction of carbon disulfide is preferably controlled to be between 5 and 60% in order to ensure the characteristics of high conductivity and low viscosity of the electrolyte.
Further, the concentration of sulfur dissolved in the electrolyte is preferably controlled to 0.05 to 10 mol/L.
For example, in a preferred embodiment, the concentration of sulfur or sulfide dissolved in the electrolyte may be 0.1-3mol/L, and the charge-discharge potential may be 1.0-3.0V.
As one of the preferable embodiments, the solvent may comprise a solvent having a volume ratio of 1: 1:1 DOL: DME: CS2。
As one of preferable specific application schemes, the preparation method of the lithium-sulfur battery can comprise the following steps:
1. the preparation method of the positive electrode comprises the following steps:
(1) coating method for preparing porous electrode
a. Selecting porous conductive materials, such as micro and mesoporous activated carbon, foamed nickel particles and the like;
b. uniformly dissolving a porous material and a binder in a solvent according to a proper proportion;
c. coating the positive electrode slurry of the step b on a positive electrode current collector;
d. and drying the solvent in vacuum, and storing for later use.
(2) Preparation of porous electrode by electrodeposition
a. Carrying out surface treatment and cleaning on the substrate of the porous anode;
b. preparing an electrodeposition solution of the porous electrode material;
c. depositing an alloy (e.g., a metal alloy such as Pt, Ni, Cu, etc.) on the electrode substrate
d. One or more components of the alloy deposited on the substrate are removed by etching.
e. And cleaning the formed porous electrode again to remove impurities on the surface, and drying for later use.
2. A method of making an anode comprising:
a. depositing an electro-deposition solution on a conductive current collector to form a lithium or lithium-containing alloy interface layer; or,
b. directly cutting lithium or lithium-containing alloy into a required shape and compounding the required shape with a battery leading-out electrode;
furthermore, an interface layer can be formed on the surface of the lithium or the lithium-containing alloy to protect the negative electrode, and the material of the interface layer is mainly a lithium ion conduction electron insulation material, such as: oxides, phosphates, fluorides, and the like.
The lithium or lithium alloy of the negative electrode may have a sheet shape or other shapes.
3. The preparation method of the electrolyte comprises the following steps:
a. a proper amount of sulfur simple substance or sulfide is dissolved in the solvent, and on the premise of ensuring high conductivity and low viscosity of the electrolyte, the higher the concentration of the active substance sulfur in the electrolyte, the better.
b. 0.5-1.5mol/L lithium salt and 0.1-0.3mol/L anode protection additive are dissolved in solvent, wherein the solvent can be one or more mixed solvents, such as DOL, DME, or other linear chain and cyclic ether solvents.
c. And (4) slowly dripping the solution in the step (a) into the electrolyte in the step (b) to ensure that the solution and the electrolyte are completely dissolved.
d. The volume ratio of the solution a to the solution b is controlled to be between 2:8 and 3: 7.
e. And (3) placing the prepared sulfur-containing electrolyte in a drying chamber or a glove box for storage.
The technical solution of the present invention is further described below with reference to several preferred embodiments.
Example 1 the positive electrode was a conductive nickel mesh, the negative electrode was a metallic lithium plate, and 2mol/L sublimed sulfur was dissolved in 30mL of an electrolyte (solvent by volume ratio DOL: DME: CS)2LiTFSI with lithium salt concentration of 1.0mol/L and LiNO of 0.2mol/L at 2:2:13) And the self-made battery with two electrodes is equipped to test the performance, the tested current is 0.5mA, and the charging and discharging range is 1.5-3.0V.
Example 2: the positive electrode was made of conductive nickel foam and the other steps were as in example 1.
Example 3: the positive electrode adopts conductive foam nickel, the tested current is 0.6,0.7,0.8,0.9 and 1.0mA, and other steps are as in example 1.
Example 4: the solvent CS2 was changed to 10%, 20%, 30% by volume in the electrolyte, and the other steps were as in example 1.
Example 5: the concentrations of active substance sulfur are respectively 0.2,0.5,1.0,1.5 and 2.0mol/L, and other steps are as shown in the examples.
Example 6: aluminum foil was used for the positive electrode, and other steps were carried out as described in examples 1 to 5.
It should be noted that, for those skilled in the art, other various changes and modifications can be made according to the technical solution and technical idea of the present invention, and these changes and modifications should fall within the protection scope of the claims of the present invention.
Claims (1)
1. A method of making a lithium-sulfur battery, comprising:
(1) providing a positive electrode comprising:
a. mixing a porous conductive material, a binder and a solvent to form anode slurry, coating the anode slurry on a current collector, and drying to form an anode; or,
b. depositing an alloy layer on the substrate by taking an electro-deposition or chemical deposition solution, and then etching to remove more than one selected alloy component and/or substrate substance in the alloy layer to form the anode with a porous structure;
(2) providing a lithium-containing anode comprising:
a. depositing an electro-deposition solution on a conductive current collector to form a lithium or lithium-containing alloy interface layer; or,
b. directly cutting lithium or lithium-containing alloy into a required shape and compounding the required shape with a battery leading-out electrode;
(3) providing an electrolyte comprising:
dissolving a sublimed sulfur simple substance in carbon disulfide, wherein the dissolving is saturated;
dissolving a negative electrode protection additive into a mixed solvent mainly formed by 1, 3-dioxolane and diethylene glycol dimethyl ether in a volume ratio of 1:1, wherein the mixed solvent contains 1M lithium salt;
taking the mixture obtained in the step i and the mixture obtained in the step ii according to the ratio of 2: 8-3: 7, and obtaining electrolyte for later use;
(4) and combining the positive electrode, the lithium-containing negative electrode and the electrolyte to form the lithium-sulfur battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310071234.0A CN103138002B (en) | 2013-03-06 | 2013-03-06 | Lithium-sulfur cell and preparation method thereof |
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| CN106340663B (en) * | 2015-07-06 | 2019-04-09 | 中国科学院大连化学物理研究所 | A kind of list liquid stream lithium-sulfur cell |
| CN105680040B (en) * | 2016-01-12 | 2019-03-29 | 浙江大学 | A kind of antimony base lithium storage materials and preparation method thereof |
| CN107623143B (en) * | 2016-07-14 | 2020-04-17 | 中国科学院上海硅酸盐研究所 | Lithium-sulfur battery electrolyte containing functional additive and application thereof |
| CN106785049A (en) * | 2016-12-21 | 2017-05-31 | 厦门大学 | A kind of lithium-sulfur cell electrolyte and its application |
| CN108899500A (en) * | 2018-06-28 | 2018-11-27 | 肇庆市华师大光电产业研究院 | A kind of preparation method of lithium sulfur battery anode material |
| CN109786829B (en) * | 2018-12-14 | 2020-06-30 | 深圳启辰新能源科技有限公司 | Lithium-sulfur battery electrolyte and preparation method thereof |
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| US5582623A (en) * | 1994-11-23 | 1996-12-10 | Polyplus Battery Company, Inc. | Methods of fabricating rechargeable positive electrodes |
| CN1423843A (en) * | 2000-02-01 | 2003-06-11 | 波利普拉斯电池有限公司 | Liquid electrolyte lithium-sulfur batteries |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5582623A (en) * | 1994-11-23 | 1996-12-10 | Polyplus Battery Company, Inc. | Methods of fabricating rechargeable positive electrodes |
| CN1423843A (en) * | 2000-02-01 | 2003-06-11 | 波利普拉斯电池有限公司 | Liquid electrolyte lithium-sulfur batteries |
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