CN116936788A - Preparation method of sulfur-based metal battery - Google Patents
Preparation method of sulfur-based metal battery Download PDFInfo
- Publication number
- CN116936788A CN116936788A CN202311106567.2A CN202311106567A CN116936788A CN 116936788 A CN116936788 A CN 116936788A CN 202311106567 A CN202311106567 A CN 202311106567A CN 116936788 A CN116936788 A CN 116936788A
- Authority
- CN
- China
- Prior art keywords
- sulfur
- source agent
- metal
- battery
- sulfide
- 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.)
- Pending
Links
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 233
- 239000011593 sulfur Substances 0.000 title claims abstract description 228
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 228
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 143
- 239000002184 metal Substances 0.000 title claims abstract description 143
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 161
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 59
- 239000011255 nonaqueous electrolyte Substances 0.000 claims abstract description 55
- 238000000034 method Methods 0.000 claims abstract description 41
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 33
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 51
- 238000010438 heat treatment Methods 0.000 claims description 46
- 229910018091 Li 2 S Inorganic materials 0.000 claims description 29
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 claims description 28
- 239000011734 sodium Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 19
- 239000007787 solid Substances 0.000 claims description 18
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 16
- 238000001914 filtration Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 10
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011244 liquid electrolyte Substances 0.000 claims description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- 239000007773 negative electrode material Substances 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 6
- JGIATAMCQXIDNZ-UHFFFAOYSA-N calcium sulfide Chemical compound [Ca]=S JGIATAMCQXIDNZ-UHFFFAOYSA-N 0.000 claims description 5
- COOGPNLGKIHLSK-UHFFFAOYSA-N aluminium sulfide Chemical compound [Al+3].[Al+3].[S-2].[S-2].[S-2] COOGPNLGKIHLSK-UHFFFAOYSA-N 0.000 claims description 4
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 150000002170 ethers Chemical class 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- QENHCSSJTJWZAL-UHFFFAOYSA-N magnesium sulfide Chemical compound [Mg+2].[S-2] QENHCSSJTJWZAL-UHFFFAOYSA-N 0.000 claims 2
- 235000009518 sodium iodide Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 27
- 239000011248 coating agent Substances 0.000 description 46
- 238000000576 coating method Methods 0.000 description 46
- 239000003054 catalyst Substances 0.000 description 44
- 239000000203 mixture Substances 0.000 description 43
- 238000004080 punching Methods 0.000 description 43
- 239000003792 electrolyte Substances 0.000 description 38
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 31
- 239000006229 carbon black Substances 0.000 description 27
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 25
- 239000002033 PVDF binder Substances 0.000 description 24
- 229910052799 carbon Inorganic materials 0.000 description 23
- 238000002156 mixing Methods 0.000 description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 19
- 239000000463 material Substances 0.000 description 18
- 239000003575 carbonaceous material Substances 0.000 description 16
- 238000007789 sealing Methods 0.000 description 15
- 229910021385 hard carbon Inorganic materials 0.000 description 13
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000011889 copper foil Substances 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 239000007774 positive electrode material Substances 0.000 description 11
- 239000011267 electrode slurry Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 230000009286 beneficial effect Effects 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000010405 anode material Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002270 dispersing agent Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 239000000956 alloy Substances 0.000 description 5
- 229910045601 alloy Inorganic materials 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000002349 favourable effect Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SMDQFHZIWNYSMR-UHFFFAOYSA-N sulfanylidenemagnesium Chemical compound S=[Mg] SMDQFHZIWNYSMR-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 2
- 239000006230 acetylene black Substances 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000011331 needle coke Substances 0.000 description 2
- 229920001021 polysulfide Polymers 0.000 description 2
- 239000005077 polysulfide Substances 0.000 description 2
- 150000008117 polysulfides Polymers 0.000 description 2
- 229910021384 soft carbon Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GQCYCMFGFVGYJT-UHFFFAOYSA-N [AlH3].[S] Chemical compound [AlH3].[S] GQCYCMFGFVGYJT-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000011366 tin-based material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- -1 uniformly mixing Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a preparation method of a sulfur-based metal battery, wherein the raw materials of the sulfur-based metal battery comprise a sulfur source agent, a metal source agent and a nonaqueous electrolyte; at least a part of the sulfur source agent and the metal source agent is dissolved in the nonaqueous electrolytic solution before or during the formation of the sulfur-based metal battery, and a saturated nonaqueous electrolytic solution containing the sulfur source agent and the metal source agent is produced. The application provides a novel sulfur-based full battery system, which not only simplifies the technological process of the sulfur-based battery, but also improves the electrochemical performance of the sulfur-based battery.
Description
The application relates to a sulfur-based metal battery and a preparation method thereof, which are divisional applications with the application number of 202211430698.1.
Technical Field
The application relates to the technical field of sulfur-based batteries, in particular to a preparation method of a sulfur-based metal battery.
Background
With the development of lithium battery technology, the development of the current commercial secondary lithium ion battery in energy density gradually approaches to the theoretical bottleneck of the secondary lithium ion battery, and further breakthrough is difficult, so that the development of a novel battery system is particularly important. The sulfur-based battery has high theoretical specific energy, has the characteristics of low price, green environmental protection and the like, and is also gradually considered as the most promising next-generation energy storage system, and the storage of elemental sulfur in the earth is extremely rich.
In a common sulfur-based battery, because the electron conductivity of elemental sulfur is poor, the elemental sulfur is sintered with a carbon material with high electron conductivity before application, and the preparation process of the sulfur-carbon composite material in the prior art is complex, so that the manufacturing cost of the sulfur-based battery is increased to a certain extent. In addition, the sulfur-based battery mainly faces five main problems at present, firstly, polysulfide compounds generated in the charge and discharge process are dissolved in electrolyte, so that active substances are reduced, the cycle performance of the battery is deteriorated, and the capacity is attenuated; second, the conductivity of sulfur is very poor, which is detrimental to the high rate performance of the battery; thirdly, the volume change of sulfur is large in the charge and discharge process, so that the stability of the battery is affected; fourth, in the conventional sulfur-based battery, the slurry formed by the sulfur-carbon composite material is required to be coated on the current collector, so as to achieve the purpose of improving the conductivity of sulfur, and since the slurry is required to satisfy sufficient fluidity so as to be uniformly coated on the current collector, the addition amount of sulfur in the slurry is limited by the preparation of the slurry, so that the original content of sulfur in the positive electrode is limited, the capacity of the battery is also greatly limited, in this case, the sulfur in the positive electrode is further consumed due to the formation of a polysulfide compound in the charge and discharge process of the prepared battery, and the circulation capacity of the battery is further reduced, so that the sulfur-based battery prepared by the conventional method is greatly limited in capacity improvement due to the limitation of the addition amount of sulfur and the circulation consumption; fifth, in the preparation process of the sulfur-based battery, for example, the lithium-sulfur battery, the pre-lithium treatment is performed to compensate the lithium loss in the first-round charge-discharge process, so as to achieve the purpose of prolonging the cycle life of the circulating battery, but the pre-lithiation process greatly increases the preparation difficulty and preparation time of the battery, and seriously affects the flow preparation process of the sulfur-based whole battery. These problems all affect the electrochemical performance of the sulfur-based battery and seriously affect the commercialization process of the sulfur-based battery.
Disclosure of Invention
Aiming at the problems in the prior art, the application discloses a novel sulfur-based metal battery, changes the composition of the sulfur-based battery, overcomes the increase of the volume of sulfur in the charging and discharging process, solves the problem that the capacity of the sulfur-based battery cannot be improved due to the limited sulfur addition, reduces the pretreatment process in the production process of the sulfur-based battery, and improves the electrochemical performance of the sulfur-based battery.
The application is realized by the following technical scheme:
the application provides a sulfur-based metal battery, which comprises a positive electrode, a negative electrode, a diaphragm, a sulfur source agent, a metal source agent and a non-aqueous electrolyte; the positive electrode comprises a positive electrode current collector and positive electrode slurry, wherein the positive electrode slurry contains a positive electrode material, and the positive electrode material comprises a host material of sulfur and sulfide; the negative electrode comprises a negative electrode current collector and negative electrode slurry, wherein the negative electrode slurry contains a negative electrode material capable of being embedded or dissolved and separated out of metal; at least a part of the sulfur source agent and the metal source agent are dissolved in the nonaqueous electrolyte before or during the battery formation to form a saturated nonaqueous electrolyte solution containing the sulfur source agent and the metal source agent, and the sulfur source agent and the metal source agent form sulfur and metal which can be respectively embedded in the positive electrode and the negative electrode during the battery formation. The metal includes a metal capable of forming a metal sulfide with sulfur.
According to the design, before or during formation of the battery, the non-aqueous electrolyte is provided with the sulfur source agent with saturation concentration and the metal source agent with saturation concentration, during formation of the battery, the sulfur source agent and the metal source agent form sulfur and metal, the sulfur and the metal are respectively embedded in the positive electrode material and the negative electrode material of the battery to form a sulfur positive electrode and a metal negative electrode, and excessive sulfur source agent and metal source agent are added to promote continuous embedding of the sulfur and the metal in the positive electrode and the negative electrode, so that the loss of the sulfur and the metal in the charging and discharging processes is compensated. The anode material selects a host material of sulfur and sulfide, can provide an embedding site for sulfur, and is favorable for overcoming the volume increase of sulfur in the charge and discharge process; the design reduces the pretreatment process of the traditional sulfur-based battery, reduces the preparation difficulty and the preparation time, and improves the electrochemical performance of the sulfur-based battery.
Further, the battery is formed to have a low power. In the formation process of the battery, the sulfur source agent and the metal source agent can be promoted to be decomposed into metal and sulfur.
As a further alternative, the low magnification is 0.05c±0.01C. The decomposition and rapid embedding of the sulfur source agent and the metal source agent are facilitated in the formation process.
As a further scheme, the state of the sulfur source agent, the metal source agent and the nonaqueous electrolyte in the battery raw material is selected from one of I-IV:
i: the nonaqueous electrolyte contains dissolved sulfur source agent and metal source agent, and exists in the form of saturated nonaqueous electrolyte solution containing the sulfur source agent and the metal source agent;
II: the sulfur source agent and the metal source agent exist in the form of undissolved particles, and the content of the sulfur source agent and the metal source agent is not less than the amount of the sulfur source agent and the metal source agent required for forming the saturated nonaqueous electrolyte solution;
III: the non-aqueous electrolyte contains dissolved sulfur source agent and metal source agent, the sulfur source agent and the metal source agent are also in undissolved particle form, and the total amount of the dissolved sulfur source agent and the metal source agent in undissolved particle form is not less than the amount of the sulfur source agent and the metal source agent required for forming the saturated non-aqueous electrolyte solution;
IV: the nonaqueous electrolyte contains a dissolved sulfur source agent and a metal source agent, and exists in the form of a saturated nonaqueous electrolyte solution containing the sulfur source agent and the metal source agent, and the sulfur source agent and the metal source agent also exist in the form of undissolved particles in the nonaqueous electrolyte solution at the same time.
As a further alternative, the above-mentioned scheme IV is preferably employed. When the nonaqueous electrolyte is added to the battery in the form of a saturated nonaqueous electrolyte solution, the nonaqueous electrolyte can be rapidly decomposed at the time of battery formation, and the formation efficiency can be improved.
As a further aspect, the host material of sulfur and sulfide includes one or more of carbon material, conductive polymer, metal oxide, porous metal material, and metal sulfide.
As a still further aspect, the host material for sulfur and sulfide is selected from carbon materials. And is more beneficial to the rapid embedding and extraction of sulfur in the carbon material.
As still further aspects, the carbon material in the positive electrode material includes one or more of porous carbon, carbon black, graphene, carbon nanotubes, carbon fibers, carbon cloth, graphite, hard carbon, coke, soft carbon, acetylene black, ketjen carbon black, carbon whiskers, and needle coke. The catalyst is used for loading sulfur, and the sulfur is embedded in the carbon material, so that a sulfur anode is formed, and the carbon material can overcome the defect that the volume of sulfur is increased.
As a further scheme, the material examples of the removable metal in the anode material are selected from carbon materials, and the metal formed by the metal source agent in the electrolyte can be loaded on the carbon materials in a removable manner; examples of the material in which the metal can be dissolved and precipitated are selected from materials capable of forming an alloy with a metal, a metal and a material capable of forming an alloy with a metal, an alloy is formed in the anode, and the alloy can be dissolved and precipitated with a metal.
As a still further aspect, the negative electrode material includes a carbon material. Because the metal is more rapidly loaded in the carbon material in a de-intercalation mode, the metal cathode is more beneficial to forming in the battery.
As still further aspects, the carbon material of the negative electrode material includes one or more of graphite, hard carbon, coke, soft carbon, acetylene black, carbon black, ketjen black, carbon whiskers, needle coke, carbon fibers, porous carbon, graphene, carbon nanotubes, and carbon cloth; the material capable of forming an alloy with a metal includes one or more of a silicon-based material, a tin-based material, and a magnesium-based material. The carbon material in the positive electrode material and the negative electrode material in the present application may be selected from the same carbon material.
As a further aspect, the sulfur source agent includes a sulfur-containing compound or elemental sulfur that is at least partially soluble in the nonaqueous electrolytic solution. Is favorable for forming sulfur in the battery formation process, and is embedded in the positive electrode material to form a sulfur positive electrode.
As a still further aspect, the sulfur source agent includes Li 2 S 2 、Li 2 S 4 、Li 2 S 6 、Li 2 S 8 、Na 2 S 2 、Na 2 S 4 、Na 2 S 6 、Na 2 S 8 One or more of lithium sulfide, sodium sulfide, potassium sulfide, calcium sulfide, tin sulfide, aluminum sulfide, magnesium sulfide and iron sulfide.
As a further aspect, the metal source agent is a compound containing a target metal that is at least partially soluble in the nonaqueous electrolytic solution.
As a still further aspect, the metal source agent includes Li 2 S 2 、Li 2 S 4 、Li 2 S 6 、Li 2 S 8 、Na 2 S 2 、Na 2 S 4 、Na 2 S 6 、Na 2 S 8 One or more of lithium sulfide, lithium iodide, sodium sulfide, magnesium sulfide, aluminum sulfide, and calcium sulfide. The metal source agent is selected, and can be added according to the type of the sulfur-based battery, for example, the sodium-sulfur battery is selected as the metal source agent capable of forming a sodium negative electrode. The metal source agent is generally further preferred to the lithium metal source agent because the lithium metal negative electrode in the lithium sulfur battery can exert better deintercalation efficiency and larger capacity.
As a still further aspect, the sulfur source agent and the metal source agent are both selected from the same group comprising Li 2 S 2 、Li 2 S 4 、Li 2 S 6 、Li 2 S 8 、Na 2 S 2 、Na 2 S 4 、Na 2 S 6 、Na 2 S 8 Lithium sulfide and sulfideOne or more of sodium. The substances can be directly embedded into the positive electrode and the negative electrode respectively after being decomposed, which is beneficial to reducing the possibility of introducing other metal or non-sulfur substances and other trace impurities into the electrolyte.
As a further aspect, the nonaqueous electrolyte contains a solvent.
As a still further aspect, the solvent comprises an organic liquid electrolyte.
As still further aspects, the organic liquid electrolyte comprises one of ethers and esters.
As still further aspects, the organic liquid electrolyte of ethers includes dimethyl ether.
As a further proposal, the specific surface area of the host material of the sulfur and sulfide is more than 20m 2 And/g. The sulfur and sulfide host material with proper specific surface area is favorable for promoting the migration and stable embedding of sulfur and overcomes the volume change of sulfur in the battery charging and discharging cycle process, so the specific surface area is larger than 20m 2 The sulfur/g host material of the sulfide is preferably.
As a further proposal, the specific surface area of the host material of the sulfur and sulfide is more than 100m 2 And/g. The specific surface area is larger, so that the positive electrode material can load more sulfur, and the first-circle specific capacity of the battery and the cycle performance of the battery are improved.
As a further scheme, the positive electrode slurry further comprises a catalyst, and the addition amount of the catalyst in the positive electrode slurry is 0.1-50 wt%.
As a still further aspect, the catalyst comprises one of a metal and a metal compound, and the catalyst has a particle size of less than 2 μm.
As still further aspects, the metal comprises one of Fe, cu, co.
As a still further aspect, the catalyst has a particle size of less than 500nm. The smaller the particle size of the catalyst, the larger the surface energy, the larger the specific surface area, and the better the catalytic effect.
As a further scheme, the addition amount of the catalyst in the positive electrode slurry is 0.1wt% to 10wt%; as still further aspects, the catalyst is added to the positive electrode slurry in an amount of 5wt% to 10wt%. The anode material can load a catalyst, so that the catalyst is more beneficial to exerting catalytic activity, and the catalyst avoids adverse effects such as poor dispersibility or side reaction and the like caused by the addition of other catalyst types in the electrolyte in a solute form in the anode; the catalyst is beneficial to reducing the energy barrier between sulfur and the positive electrode material when the battery is in the formation process, so that the sulfur is promoted to be embedded in the positive electrode material; meanwhile, during the charge and discharge of the battery, the reaction between sulfur and metal is promoted.
As a further scheme, the positive electrode slurry of the battery also comprises an adhesive, a positive electrode conductive agent and a positive electrode dispersing agent, and the negative electrode slurry of the battery also comprises an adhesive, a negative electrode conductive agent and a negative electrode dispersing agent.
As a further scheme, the mass ratio of the positive electrode material to the binder to the positive electrode conductive agent is 8:1:1.
As a further scheme, the mass ratio of the anode material, the binder and the anode conductive agent is 94:3:3.
The application also provides a preparation method of the sulfur-based metal battery, which comprises the following steps:
s1: adding a positive electrode material, a binder and a positive electrode conductive agent into a dispersing agent according to the mass ratio, adding a catalyst, uniformly mixing, coating on a positive electrode current collector, and heating to obtain a positive electrode;
s2: adding a negative electrode material, an adhesive and a negative electrode conductive agent into a dispersing agent according to the mass ratio, uniformly mixing, coating on a negative electrode current collector, and heating to obtain a negative electrode;
s3: the preparation of the nonaqueous electrolyte, and then the assembly of the sulfur-based metal battery are carried out, wherein the specific method is one of I-IV:
i: adding excessive sulfur source agent and metal source agent into the organic liquid electrolyte, wherein the addition mass of the sulfur source agent and the metal source agent is not lower than the mass of the sulfur source agent and the metal source agent which can form saturated nonaqueous electrolyte solution in the nonaqueous electrolyte; heating and stirring, dissolving to form a non-aqueous electrolyte of a sulfur source agent and a metal source agent with saturated concentrations, and filtering; assembling a soft-package battery by taking the positive electrode plate, the diaphragm and the negative electrode plate, adding the obtained organic liquid electrolyte into the soft-package battery, and sealing;
II: the method comprises the steps of assembling a soft package battery by using a positive electrode plate, a diaphragm and a negative electrode plate, adding excessive sulfur source agent and metal source agent solid particles into the soft package, wherein the addition mass of the sulfur source agent solid particles and the metal source agent solid particles is not lower than the mass of a saturated nonaqueous electrolyte solution formed by the sulfur source agent and the metal source agent in the nonaqueous electrolyte; adding organic liquid electrolyte into the soft package battery, and sealing;
III: adding a sulfur source agent and a metal source agent into the organic liquid electrolyte, heating and stirring, and dissolving to form a non-aqueous electrolyte containing the sulfur source agent and the metal source agent; assembling a soft-package battery by taking a positive electrode plate, a diaphragm and a negative electrode plate, adding sulfur source agent solid particles and metal source agent solid particles into the soft package, adding the obtained nonaqueous electrolyte into the soft-package battery, and sealing; the total added mass of the dissolved sulfur source agent and the metal source agent and the undissolved sulfur source agent solid particles and the metal source agent solid particles in the nonaqueous electrolytic solution is not lower than the mass of the sulfur source agent and the metal source agent capable of forming a saturated nonaqueous electrolytic solution in the nonaqueous electrolytic solution;
IV: adding excessive sulfur source agent and metal source agent into the organic liquid electrolyte, wherein the addition mass of the sulfur source agent and the metal source agent is not lower than the mass of the sulfur source agent and the metal source agent which can form saturated nonaqueous electrolyte solution in the nonaqueous electrolyte; heating and stirring, dissolving to form a non-aqueous electrolyte of a sulfur source agent and a metal source agent with saturated concentrations, and filtering; assembling a soft-package battery by taking a positive electrode plate, a diaphragm and a negative electrode plate, adding sulfur source agent solid particles and metal source agent solid particles which are not less than 0g into the soft package, adding the obtained nonaqueous electrolyte into the soft-package battery, and sealing;
s4: and (3) forming the assembled battery, and performing charge and discharge test on the formed battery.
As a further scheme, the binder in the S1 is PVDF (polyvinylidene fluoride), the positive electrode conductive agent is carbon black, the positive electrode dispersing agent is NMP (N-methyl pyrrolidone), the positive electrode current collector is aluminum foil, and the thickness of the coating is 90-110 mu m; the heating temperature is 70-90 ℃ and the heating time is 7-9 h; the adhesive in the S2 is PVDF, the negative electrode conductive agent is carbon black, the negative electrode dispersing agent is NMP, the negative electrode current collector is copper foil, and the thickness of the coating is 90-110 mu m; the heating temperature is 70-90 ℃ and the heating time is 7-9 h; and in the step S3, the heating and stirring temperature is 50-70 ℃, and the heating and stirring time is 70-80 h.
The application has the characteristics and beneficial effects that:
(1) The application provides a novel sulfur-based full battery system, which simplifies the technological process of the sulfur-based battery, reduces the production time of the sulfur-based battery and the production difficulty, and is beneficial to forming a sulfur-based battery production line.
(2) The application is not limited to lithium sulfur batteries, sodium sulfur batteries, magnesium sulfur batteries, aluminum sulfur batteries, and calcium sulfur batteries.
(3) The method for decomposing the sulfur source agent and the metal source agent is used, so that sulfur and metal in the nonaqueous electrolyte are continuously inlaid in the positive electrode and the negative electrode, the consumption of the sulfur and the metal in the charging and discharging processes of the battery is made up, and the capacity of the sulfur-based battery is improved.
(4) The dilemma of limited sulfur addition in the sulfur-based battery is solved, thereby improving the capacity and cycle performance of the sulfur-based battery.
(5) The host materials of sulfur and sulfide are porous carbon, and the generated sulfur is embedded in the porous carbon, so that the volume change of sulfur in the charging and discharging processes is overcome.
(6) The sulfur-based metal battery provided by the application has the advantages that before battery formation, the positive electrode is not limited to carry sulfur, the negative electrode is not limited to contain metal, the sulfur-based metal battery is especially suitable for sulfur-free positive electrodes and metal-free negative electrodes, the technical process for preparing the sulfur positive electrodes and the metal negative electrodes is reduced, and the electrochemical performance of the sulfur-based battery is improved.
Detailed Description
In order to facilitate understanding of one of the present application, a more complete description of one of the present application is provided below, and examples of the present application are given, without thereby limiting the scope of the present application.
Example 1
(1) Preparation of positive electrode plate
Will have a specific surface area of 50m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1 respectively, uniformly mixing, coating on aluminum foil with the coating thickness of 100 mu m, heating at 80 ℃ for 8 hours, and punching by a sheet punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 2
(1) Preparation of positive electrode plate
Will have a specific surface area of 100m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1 respectively, uniformly mixing, coating on aluminum foil with the coating thickness of 100 mu m, heating at 80 ℃ for 8 hours, and punching by a sheet punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 3
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1 respectively, uniformly mixing, coating on aluminum foil with the coating thickness of 100 mu m, heating at 80 ℃ for 8 hours, and punching by a sheet punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 4
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Per gram of porous carbon,PVDF and carbon black (Super P) are respectively added into NMP according to the mass ratio of 8:1:1, then catalyst copper powder (particle size of 2 mu m) with the mass fraction of 0.5wt% is added, after uniform mixing, the mixture is coated on aluminum foil, the coating thickness is 100 mu m, and after heating for 8 hours at 80 ℃, the mixture is punched by a punching machine for standby.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 5
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1, adding catalyst copper powder (particle size of 500 nm) with the mass fraction of 0.5wt%, uniformly mixing, coating on aluminum foil, coating thickness of 100 μm, heating at 80 ℃ for 8 hours, and punching by a sheet punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
2.3g of lithium sulfide and 4.8g of sulfur were added to 10mLHeating and stirring in DME solution at 60deg.C for 72 hr, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 6
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1, adding catalyst copper powder (particle size of 100 nm) with the mass fraction of 0.5wt%, uniformly mixing, coating on aluminum foil, coating thickness of 100 μm, heating at 80 ℃ for 8 hours, and punching by a sheet punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 7
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Porous carbon, PVDF, carbon black (Super P) in mass ratio per gramAdding the mixture into NMP in a ratio of 8:1:1 respectively, adding catalyst copper powder (particle size of 100 nm) with a mass fraction of 5wt%, uniformly mixing, coating the mixture on aluminum foil with a coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 8
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1 respectively, adding catalyst copper powder (particle size of 100 nm) with the mass fraction of 10wt%, uniformly mixing, coating on aluminum foil, coating thickness of 100 mu m, heating at 80 ℃ for 8 hours, and punching by a punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
2.3g of lithium sulfide and 4.8g of sulfur were added to 10mL of DME solution, heated and stirred at 60℃for 72h and cooledHowever, a saturated Li is obtained after filtration with filter paper 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And (5) sealing after electrolyte. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Example 9
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 Adding per gram of porous carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1 respectively, adding catalyst copper powder (particle size of 100 nm) with the mass fraction of 10wt%, uniformly mixing, coating on aluminum foil, coating thickness of 100 mu m, heating at 80 ℃ for 8 hours, and punching by a punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
3.9g of sodium sulfide and 4.8g of sulfur were added to 10mL of DME solution, heated and stirred at 60℃for 72 hours, cooled, and filtered with filter paper to give a saturated Na 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of sodium sulfide particles into the soft package; 2g of saturated Na was added 2 S 4 And sealing after the electrolyte is electrolyzed. The battery was formed at 0.05C rate. And carrying out charge and discharge test on the battery after formation.
Comparative example 1
(1) Preparation of positive electrode plate
Will have a specific surface area of 200m 2 The porous carbon, PVDF and carbon black (Super P) are added into NMP according to the mass ratio of 8:1:1, and thenAdding 10wt% copper powder (particle size of 100 nm), mixing, coating on aluminum foil with thickness of 100 μm, heating at 80deg.C for 8 hr, and punching with a sheet punching machine.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(4) Battery preparation
Assembling a soft package battery by taking the positive pole piece, the diaphragm and the negative pole piece, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And sealing after the electrolyte is electrolyzed. And performing charge and discharge tests.
Comparative example 2
(1) Preparation of sulfur-carbon positive electrode plate
Respectively adding a sulfur-carbon positive electrode (the mass ratio of sulfur to carbon is 3:1), PVDF and carbon black (Super P) into NMP according to the mass ratio of 8:1:1, coating the mixture on an aluminum foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(2) Preparation of negative electrode plate
Adding hard carbon, PVDF and carbon black (Super P) into NMP according to the mass ratio of 94:3:3 respectively, uniformly mixing, coating the mixture on a copper foil with the coating thickness of 100 mu m, heating the mixture at 80 ℃ for 8 hours, and punching the mixture by a punching machine for later use.
(3) Preparation of pre-lithiated negative electrode plate
And (3) placing the negative electrode plate, dropwise adding 4g of electrolyte (1M LiTFSI-DOL/DME (5:5vol)), placing a lithium belt with a size slightly larger than that of the electrode plate and a thickness of 120 mu M, placing the lithium belt under high pressure for 48 hours, and removing the lithium plate to obtain the pre-lithiated negative electrode plate.
(4) Preparation of saturated electrolyte
Adding 2.3g of lithium sulfide and 4.8g of sulfur into 10mL of DME solution, heating and stirring at 60 ℃ for 72 hours, cooling, and filtering with filter paper to obtain saturated Li 2 S 4 Is used as an electrolyte.
(5) Battery preparation
Assembling a soft package battery by taking a positive electrode plate, a diaphragm and a pre-lithiated negative electrode plate, and adding 0.1g of lithium sulfide particles into the soft package; 2g of saturated Li is added 2 S 4 And sealing after the electrolyte is electrolyzed. And performing charge and discharge tests.
Verification result analysis
Table 1 example and comparative example parameters and battery performance
We have experimentally compared the effects of the specific surface areas of the host materials of sulfur and sulfide of different specific surface areas, the content of catalyst, and the particle size of the catalyst on the capacity of the resulting sulfur-based battery, and thus obtained the optimal preparation method of the sulfur-based battery, as shown in examples 1 to 9.
We first studied the effect of sulfur and sulfide host materials of different specific surface areas on the capacity of sulfur-based batteries, as shown in examples 1-3. The specific surface area of the carbon material is increased, so that the first-circle specific capacity and the capacity retention rate of the battery are increased, and the specific surface area is larger, so that more sulfur can be loaded and generated by carbon, and the first-circle specific capacity and the cycle performance of the battery are improved. We further selected that the specific surface area of the host material of sulfur and sulfide is greater than 100m 2 /g。
We have studied the effect of the catalyst on the electrochemical performance of the sulfur-based battery, and the addition of the catalyst to the battery is advantageous in improving the cycle performance of the sulfur-based battery, as compared with examples 4-8 and examples 1-3. The first circle specific capacity and the capacity retention rate of the sulfur-based battery added with the catalyst are both superior to those of the sulfur-based battery without the catalyst, the catalyst is added in the positive electrode plate, the catalytic activity of the catalyst can be enhanced firstly, the carbon material is porous carbon, the catalyst is dispersed, the catalytic activity of the catalyst is improved more favorably, the energy barrier between sulfur and carbon can be reduced, the generated sulfur can be quickly embedded in the porous carbon in the battery formation process, so that a sulfur positive electrode is formed, and the catalyst can promote the charge transfer between the sulfur and metal in the battery heavy discharge process, so that the electrochemical rate of charge and discharge of the battery is improved, and the specific capacity and the capacity retention rate of the battery are improved. On this basis, we have studied the effect of the particle size of the catalyst on the catalytic effect, as shown in examples 4-6. When the particle diameter of the catalyst is smaller, both the first-turn specific capacity and the capacity retention rate of the battery are increased, and it is considered that it is possible that the smaller the particle diameter of the catalyst is, the larger the surface energy is, the larger the specific surface area is, the better the catalytic effect is, and we further select the particle diameter of the catalyst to be smaller than 500nm. In addition, the addition amount of the catalyst also affects the capacity of the sulfur-based battery, and as the catalyst addition amount increases, the first-pass specific capacity and the capacity retention rate of the sulfur-based battery increase, as shown in example 6-example 8, we consider that the increase in the catalyst addition amount increases more active sites, but that too much catalyst addition amount may affect the addition amount of other substances in the positive electrode, and that the cost of the catalyst is high, and that the addition amount also needs to be considered. In summary, we further selected that the catalyst was added in an amount of 0.1wt% to 10wt%. When the catalyst addition amount is 5wt% to 10wt%, the catalytic effect is optimal, and we further select the catalyst addition amount to be 5wt% to 10wt%.
Li in nonaqueous electrolyte + Lithium is formed in the battery formation process and is embedded in the anode material, and if the particle size of the embedded particles is increased, the difficulty of embedding is increased, the number of embedded particles is reduced, and the battery capacity is reduced. As shown in example 9, sodium sulfide and sulfur were added to the nonaqueous electrolyte, and sodium ions had a larger diameter than lithium ions, resulting in a greater difficulty in the transport and deintercalation of ions on the negative electrode material, resulting in a significant decrease in the first-ring specific capacity of the battery of example 9, and a significant decrease in the first-ring specific capacity of the battery of example 8The capacity is about 3 times that of example 9.
The prepared sulfur-based battery is subjected to formation at the rate of 0.05C, so that the sulfur source agent and the metal source agent in the nonaqueous electrolyte are decomposed to form sulfur and metal which are respectively embedded in the anode material and the cathode material of the battery, and a metal cathode and a sulfur anode are formed. The preparation method can overcome the volume change of sulfur in the charge and discharge process, thereby improving the conductivity of sulfur, and can add excessive sulfur source agent and metal source agent, thereby realizing continuous inlay of sulfur and metal in the anode and the cathode, and overcoming the problem of reduced battery capacity caused by the loss of sulfur and metal. As shown in example 8 and comparative example 1, the first-turn specific capacity of the battery of example 8 was 15 times that of the battery of comparative example 1. Therefore, the formation is favorable for the formation of a metal negative electrode and a sulfur positive electrode of the sulfur-based battery, the capacity of the battery is improved, and the first-circle specific capacity of the battery is obviously increased.
On this basis, the sulfur-based battery prepared by the present application was compared with the sulfur-based battery prepared by the conventional method, as in example 8 and comparative example 2. The first-circle specific capacity and the capacity retention rate of the sulfur-based battery prepared by the method are superior to those of the traditional method, and the method can reduce the technical process of the negative electrode plate, such as the pre-lithiation process of the lithium-sulfur battery, thereby greatly reducing the preparation difficulty and the preparation time, and being beneficial to designing a production line for the streamline preparation of the sulfur-based battery.
In summary, the novel sulfur-based full battery system not only simplifies the process flow of the production of the sulfur-based battery, but also improves the electrochemical performance of the sulfur-based battery.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present application, and are not intended to limit the present application, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (10)
1. A method for producing a sulfur-based metal battery, characterized in that a raw material of the sulfur-based metal battery comprises a sulfur source agent, a metal source agent and a nonaqueous electrolyte; at least a part of the sulfur source agent and the metal source agent is dissolved in the nonaqueous electrolytic solution before or during the formation of the sulfur-based metal battery, and a saturated nonaqueous electrolytic solution containing the sulfur source agent and the metal source agent is produced.
2. The production method according to claim 1, wherein the specific production method for dissolving at least a part of the sulfur source agent and the metal source agent in the nonaqueous electrolytic solution and producing the saturated nonaqueous electrolytic solution containing the sulfur source agent and the metal source agent before or during the formation of the sulfur-based metal battery is selected from one of the group consisting of i to iv:
i: adding excessive sulfur source agent and metal source agent into the non-aqueous electrolyte, wherein the addition mass of the sulfur source agent and the metal source agent is not lower than the mass of the sulfur source agent and the metal source agent which can form saturated non-aqueous electrolyte solution in the non-aqueous electrolyte; heating and stirring, dissolving to form saturated nonaqueous electrolyte of sulfur source agent and metal source agent, filtering, and injecting;
II: injecting the nonaqueous electrolyte, and then adding excessive sulfur source agent and metal source agent solid particles into the nonaqueous electrolyte, wherein the addition mass of the sulfur source agent solid particles and the metal source agent solid particles is not lower than the mass of the sulfur source agent and the metal source agent forming saturated nonaqueous electrolyte solution in the nonaqueous electrolyte;
III: adding a sulfur source agent and a metal source agent into the nonaqueous electrolyte, heating and stirring, and dissolving to form a non-saturated nonaqueous electrolyte containing the sulfur source agent and the metal source agent, and injecting the solution; then adding sulfur source agent solid particles and metal source agent solid particles into the unsaturated nonaqueous electrolyte; the total added mass of the dissolved sulfur source agent and the metal source agent and the undissolved sulfur source agent solid particles and the metal source agent solid particles in the non-saturated non-aqueous electrolyte is not lower than the mass of the sulfur source agent and the metal source agent capable of forming a saturated non-aqueous electrolyte solution in the non-aqueous electrolyte;
IV: adding excessive sulfur source agent and metal source agent into the non-aqueous electrolyte, wherein the addition mass of the sulfur source agent and the metal source agent is not lower than the mass of the sulfur source agent and the metal source agent which can form saturated non-aqueous electrolyte solution in the non-aqueous electrolyte; heating and stirring, dissolving to form non-aqueous electrolyte of sulfur source agent and metal source agent with saturated concentration, filtering, and injecting liquid; and adding sulfur source agent solid particles and metal source agent solid particles which are not less than 0g into the saturated nonaqueous electrolyte.
3. The preparation method according to claim 2, wherein the temperature of heating and stirring in I, III and IV is 50-70 ℃, and the time of heating and stirring is 70-80 h.
4. The method according to claim 1, wherein the sulfur-based metal battery is formed into a low-rate formation, the low-rate formation being 0.05c±0.01C.
5. The method according to claim 1, wherein the sulfur source agent is a sulfur-containing compound or elemental sulfur which is at least partially soluble in the nonaqueous electrolytic solution; the metal source agent is a compound containing a target metal that is at least partially soluble in a nonaqueous electrolytic solution;
further preferably, the sulfur source agent comprises one or more of lithium sulfide, sodium sulfide, potassium sulfide, calcium sulfide, tin sulfide, aluminum sulfide, magnesium sulfide, and iron sulfide; the metal source agent comprises one or more of lithium sulfide, sodium sulfide, lithium iodide, sodium iodide, magnesium sulfide, aluminum sulfide and calcium sulfide.
6. The method of claim 5, wherein the sodium sulfide comprises Na 2 S 2 、Na 2 S 4 、Na 2 S 6 、Na 2 S 8 One or more of the following; the lithium sulfide includes Li 2 S 2 、Li 2 S 4 、Li 2 S 6 、Li 2 S 8 One or more of the following.
7. The method according to claim 5, wherein the sulfur source agent and the metal source agent are selected from the same group consisting of lithium sulfide and sodium sulfide;
further preferably, the sodium sulfide includes Na 2 S 2 、Na 2 S 4 、Na 2 S 6 、Na 2 S 8 One or more of the following; the lithium sulfide includes Li 2 S 2 、Li 2 S 4 、Li 2 S 6 、Li 2 S 8 One or more of the following.
8. The method according to claim 1, wherein the nonaqueous electrolytic solution comprises an organic liquid electrolytic solution, and the organic liquid electrolytic solution comprises one of ethers and esters; the organic liquid electrolyte of the ether comprises dimethyl ether.
9. The method according to claim 1, wherein the method comprises a step of dissolving at least a part of the sulfur source agent and the metal source agent in the nonaqueous electrolytic solution before or during the formation of the sulfur-based metal battery to form a saturated nonaqueous electrolytic solution containing the sulfur source agent and the metal source agent, and a step of forming the sulfur-based metal battery.
10. The method according to claim 9, wherein the positive electrode contains no sulfur and the negative electrode material contains no metal before the sulfur-based metal battery is formed;
further preferably, in the sulfur-based metal battery formation, at least a part of the sulfur source agent and the metal source agent form sulfur and metal from the saturated nonaqueous electrolyte solution and are respectively embedded in the positive electrode and the negative electrode;
further preferably, the metal comprises lithium or sodium.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311106567.2A CN116936788A (en) | 2022-11-16 | 2022-11-16 | Preparation method of sulfur-based metal battery |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211430698.1A CN115498174B (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery and preparation method thereof |
| CN202311106567.2A CN116936788A (en) | 2022-11-16 | 2022-11-16 | Preparation method of sulfur-based metal battery |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211430698.1A Division CN115498174B (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116936788A true CN116936788A (en) | 2023-10-24 |
Family
ID=85116347
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311106567.2A Pending CN116936788A (en) | 2022-11-16 | 2022-11-16 | Preparation method of sulfur-based metal battery |
| CN202211430698.1A Active CN115498174B (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery and preparation method thereof |
| CN202311106551.1A Pending CN116885160A (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211430698.1A Active CN115498174B (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery and preparation method thereof |
| CN202311106551.1A Pending CN116885160A (en) | 2022-11-16 | 2022-11-16 | Sulfur-based metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (3) | CN116936788A (en) |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6358643B1 (en) * | 1994-11-23 | 2002-03-19 | Polyplus Battery Company | Liquid electrolyte lithium-sulfur batteries |
| JP2005158313A (en) * | 2003-11-21 | 2005-06-16 | Sanyo Electric Co Ltd | Non-aqueous electrolyte secondary battery |
| CN102983361B (en) * | 2012-11-23 | 2015-04-22 | 中国人民解放军国防科学技术大学 | Electrolyte for Li-S battery, preparation method thereof, and Li-S battery containing same |
| CN108539265A (en) * | 2017-03-02 | 2018-09-14 | 深圳格林德能源有限公司 | A kind of lithium-sulfur cell |
| CN109841425B (en) * | 2017-11-27 | 2021-10-15 | 中国科学院大连化学物理研究所 | Capacitor battery and preparation method thereof |
-
2022
- 2022-11-16 CN CN202311106567.2A patent/CN116936788A/en active Pending
- 2022-11-16 CN CN202211430698.1A patent/CN115498174B/en active Active
- 2022-11-16 CN CN202311106551.1A patent/CN116885160A/en active Pending
Also Published As
| Publication number | Publication date |
|---|---|
| CN115498174A (en) | 2022-12-20 |
| CN116885160A (en) | 2023-10-13 |
| CN115498174B (en) | 2023-08-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110112475B (en) | Sodium ion battery positive electrode containing sodium supplement additive and preparation method and application thereof | |
| CN111029569B (en) | Lithium ion battery lithium supplementing additive, battery electrode, preparation method and application thereof | |
| CN108232343A (en) | Benefit lithium additive, benefit lithium anode and its preparation and application for lithium ion battery | |
| CN110148739B (en) | Carbon @ vulcanized acrylonitrile-based polymer composite positive electrode active material, positive electrode, preparation method of positive electrode and application of positive electrode in lithium-sulfur battery | |
| CN108321438B (en) | Full-graphite lithium-sulfur battery and preparation method thereof | |
| CN103346304A (en) | Tin-carbon composite material for lithium secondary battery negative electrode and preparation method thereof | |
| CN107140633A (en) | A kind of preparation method and applications of the activated carbon with high specific surface area of biomass derived | |
| CN109411719B (en) | Titanium carbide/titanium dioxide-sulfur ternary composite positive electrode material, preparation method and application thereof, and lithium-sulfur battery | |
| CN114944476B (en) | MoS (MoS) 2 /Fe 2 O 3 Heterostructure @ porous carbon fiber composite material and preparation method and application thereof | |
| CN113501511B (en) | Method for adjusting nitrogen-doped carbon structure based on phytic acid and application of method | |
| CN114204027A (en) | Lithium ion battery positive pole piece, preparation method thereof and lithium ion battery | |
| CN108767203B (en) | Titanium dioxide nanotube-graphene-sulfur composite material and preparation method and application thereof | |
| CN112635726A (en) | Bentonite-based composite material and preparation method and application thereof | |
| WO2020034875A1 (en) | Sulfur-based positive electrode active material for use in solid-state battery, preparation for material, and applications thereof | |
| CN113066988B (en) | Negative pole piece and preparation method and application thereof | |
| CN111705315B (en) | Preparation method of modified copper three-dimensional framework and application of modified copper three-dimensional framework in lithium battery | |
| CN115498174B (en) | Sulfur-based metal battery and preparation method thereof | |
| CN115784223A (en) | High-sulfur Jiao Ji quick-charging graphite active material, preparation thereof and application thereof in lithium ion battery | |
| CN111146438A (en) | Positive active material, preparation method thereof, battery positive plate and lithium battery | |
| WO2018195837A1 (en) | Metal-sulfur battery and preparation method therefor | |
| CN110048060B (en) | Graphene oxide loaded column pentaarene lithium-sulfur battery diaphragm, preparation method and application thereof | |
| CN113328076A (en) | Carbon-coated iron sulfide quantum dot composite nanosheet and preparation method and application thereof | |
| CN117199360B (en) | Sodium carbonate/carbon composite positive electrode sodium supplementing additive, preparation method thereof and application thereof in negative electrode-free sodium metal battery | |
| CN109192967A (en) | A kind of preparation method and application of lithium-sulphur cell positive electrode | |
| CN114512632B (en) | Positive electrode plate for lithium-sulfur battery and preparation method thereof |
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 |