CN117199382A - Dual-functional current collector, preparation method thereof and lithium-sulfur battery - Google Patents
Dual-functional current collector, preparation method thereof and lithium-sulfur battery Download PDFInfo
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- CN117199382A CN117199382A CN202311066580.XA CN202311066580A CN117199382A CN 117199382 A CN117199382 A CN 117199382A CN 202311066580 A CN202311066580 A CN 202311066580A CN 117199382 A CN117199382 A CN 117199382A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- -1 transition metal cation Chemical class 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 10
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 239000004744 fabric Substances 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 230000020477 pH reduction Effects 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012495 reaction gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229920000742 Cotton Polymers 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 238000010306 acid treatment Methods 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims 1
- 229910052744 lithium Inorganic materials 0.000 abstract description 29
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 19
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 10
- 230000008021 deposition Effects 0.000 abstract description 9
- 239000013543 active substance Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical group [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 230000001939 inductive effect Effects 0.000 abstract description 2
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- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000000151 deposition Methods 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 239000002135 nanosheet Substances 0.000 description 6
- 150000001721 carbon Chemical class 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 4
- 210000001787 dendrite Anatomy 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- 239000004809 Teflon Substances 0.000 description 3
- 229920006362 Teflon® Polymers 0.000 description 3
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- 230000000996 additive effect Effects 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
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- 239000010431 corundum Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 2
- 229910018091 Li 2 S Inorganic materials 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NGKWYRANVWGTGG-UHFFFAOYSA-N [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Ni++].CO.[O-][N+]([O-])=O.[O-][N+]([O-])=O NGKWYRANVWGTGG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
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- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000005077 polysulfide Substances 0.000 description 1
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a difunctional current collector, a preparation method thereof and a lithium-sulfur battery. The preparation method of the dual-function current collector comprises the following steps: and placing the acidified three-dimensional carbon matrix in a transition metal cation salt solution for hydrothermal reaction, drying to obtain a precursor, and carrying out phosphating treatment on the precursor to obtain the dual-function current collector. The dual-function current collector can be used as a positive current collector or a negative current collector of a battery, has the property of a lithium-philic atom and is used for inducing uniform deposition of lithium ions, so that the coulomb efficiency of a dendrite-free lithium negative electrode is improved, the cycle life of the battery is prolonged, the dual-function current collector has high-efficiency adsorption and catalysis effects on sulfur-containing active substances, the reaction kinetics of the battery can be improved, the utilization rate of positive sulfur is improved, and the dual-function current collector has certain promotion and guidance effects on development of a battery with high energy density and high stability.
Description
Technical Field
The invention belongs to the field of lithium-sulfur batteries, and relates to a difunctional current collector, a preparation method thereof and a lithium-sulfur battery.
Background
At present, development and utilization of clean energy become more and more urgent, and traditional lithium ion batteries based on graphite negative electrodes have difficulty in meeting the requirements of rapid development of electric automobiles and smart grid technologies. High capacityThe negative electrode is an electrode material that is urgently required to be developed for the next-generation high-energy-density battery system. Lithium metal has a high theoretical specific capacity (3860 mAh.g -1 ) Lowest redox potential (3.04V relative to standard hydrogen electrode) and low density (0.59 g cm) -3 ) The "holy cup" material as the negative electrode of the battery continues to receive extensive attention from researchers. Lithium metal is used as the negative electrode, and the positive electrode is matched with elemental sulfur (specific capacity 1675 mAh.g -1 ) The lithium sulfur battery of (2) has much higher energy density than commercial lithium batteries, and is the focus of research on new generation secondary batteries. The sulfur element needed by the anode is stored in the crust, and the exploitation technology is mature and low in cost. These advantages make the development and popularization of lithium-sulfur batteries have obvious advantages of performance, resources and cost.
However, due to the physicochemical properties of the positive electrode sulfur and the negative electrode lithium, and the complicated electrochemical reaction process, the lithium sulfur battery has a plurality of technical problems, so that the commercialized application of the lithium sulfur battery faces a plurality of challenges. First, the positive electrode has problems of "shuttling effect" caused by insulation of the active material, expansion of discharge volume, and dissolution of lithium polysulfide (LiPS), which are affected by the physicochemical properties of the sulfur-containing active material of the positive electrode. Secondly, active lithium metal as a negative electrode is generally subject to problems such as volume expansion, lithium dendrite growth, "dead lithium" and unstable solid electrolyte layers (SEI). In addition, in order to achieve the goal of high energy density, lithium sulfur batteries are required to meet more requirements, including high sulfur content>70 wt.%), high surface sulfur loading%>5mg·cm -2 ) Low negative to positive capacity ratio (low N/P ratio), and lean electrolyte (low E/S ratio), etc., which also exposes the above problems more significantly.
CN110911682a discloses an electrode of lithium sulfur battery, its preparation method and application. The electrode of the lithium-sulfur battery comprises a current collector, wherein a microcrack carbon nano tube layer, an active material layer, a carbon nano tube and a lithium titanate composite coating are sequentially arranged on the surface of the current collector, but the preparation method of the electrode is too complex, the number of layers is too large, the cost is high, and the large-scale production is not facilitated.
CN113594415a discloses a sandwich independent anode for inhibiting shuttle effect of lithium-sulfur battery and its preparation method. The porous carbon fiber membrane embedded with cobalt nano particles replaces the traditional aluminum foil, has the function of a current collector, and the conductive net structure of the porous carbon fiber membrane increases the contact area with active substances and can reduce pulverization and falling of materials. However, the substitution of the conventional aluminum foil with cobalt nanoparticle-embedded porous carbon fibers is not suitable for industrial mass production, and is only suitable for laboratory researches at present.
Therefore, how to industrially and simply prepare a current collector capable of inhibiting the shuttle effect of a lithium-sulfur battery and improving the electrochemical performance of the battery is an important research direction in the field.
Disclosure of Invention
The invention aims to provide a difunctional current collector, a preparation method thereof and a lithium-sulfur battery, wherein the difunctional current collector can be used for both sides of a positive electrode and a negative electrode of the battery, has the property of a lithium-philic atom and is used for inducing uniform deposition of lithium ions, so that the coulomb efficiency of a dendrite-free lithium negative electrode is improved, and the cycle life of the battery is prolonged; the dual-function current collector has high-efficiency adsorption and catalysis effects on sulfur-containing active substances, can improve the reaction kinetics of the battery and the utilization rate of positive electrode sulfur, and has certain promotion and guidance effects on the development of high-energy-density high-stability batteries.
The invention aims at providing a preparation method of a dual-function current collector, which comprises the following steps:
and placing the acidified three-dimensional carbon matrix in a transition metal cation salt solution for hydrothermal reaction, drying to obtain a precursor, and carrying out phosphating treatment on the precursor to obtain the dual-function current collector.
The three-dimensional carbon matrix is a three-dimensional carbon material with high specific surface area, and the three-dimensional carbon material with high specific surface area is subjected to matrix surface modification, so that the conductivity of a battery can be effectively improved, the volume expansion of an electrode in a charging and discharging process can be relieved, the current density of a negative electrode can be reduced, the growth of lithium dendrites can be relieved, the effects of sulfur fixation and the lithium affinity of the current collector can be effectively considered, the dual-function current collector can be used on both sides of the positive electrode and the negative electrode of the battery, and the performance of the positive electrode and the negative electrode of the battery can be improved.
The dual-function current collector can effectively improve the utilization rate of anode sulfur in the lithium sulfur battery, accelerate LiPS conversion, reduce the N/P ratio, improve the stability of a lithium metal cathode and realize the high energy density of the lithium sulfur battery.
As a preferred technical scheme of the invention, the acidification is to soak the three-dimensional carbon matrix in an acidic solution for acidification.
Preferably, the acidification is followed by a first wash with water until the wash is neutral.
Preferably, the three-dimensional carbon matrix comprises any one of commercial carbon cloth, carbon paper, carbonized cotton cloth or coaxial spun carbon film.
Preferably, the acidic solution comprises a nitric acid solution.
Preferably, the concentration of the nitric acid solution is 2-4M, wherein the concentration may be 2M, 2.2M, 2.4M, 2.6M, 2.8M, 3.0M, 3.2M, 3.4M, 3.6M, 3.8M or 4M, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the acidification is performed in a reaction kettle.
Preferably, the acidification temperature is 140 to 160 ℃, wherein the temperature can be 140 ℃, 142 ℃, 144 ℃, 146 ℃, 148 ℃, 150 ℃, 152 ℃, 154 ℃, 156 ℃, 158 ℃, 160 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the acidification time is 5 to 7 hours, wherein the time may be 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6.0 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours or 7 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferred embodiment of the present invention, the solvent for the hydrothermal reaction comprises any one or a combination of at least two of deionized water, methanol, ethanol or DMF, wherein typical but non-limiting examples of the combination are: a combination of water and methanol, a combination of methanol and ethanol, or a combination of ethanol and DMF, etc.
Preferably, the transition metal cation salt in the transition metal cation salt solution comprises any one or a combination of at least two of ferric nitrate, nickel nitrate, cobalt nitrate, ferric chloride, nickel sulfate or cobalt acetate, wherein typical but non-limiting examples of the combination are: a combination of iron nitrate and nickel nitrate, a combination of nickel nitrate and cobalt nitrate, a combination of cobalt nitrate and iron chloride, a combination of iron chloride and nickel sulfate, or a combination of nickel sulfate and cobalt acetate, and the like.
Preferably, the hydrothermal reaction further comprises an additive.
Preferably, the additive comprises any one or a combination of at least two of ammonium fluoride, urea or urotropin, typical but non-limiting examples of which are: a combination of ammonium fluoride and urea, a combination of urea and urotropine, or a combination of ammonium fluoride and urotropine, and the like.
The additive is used for controlling the appearance of the product.
In a preferred embodiment of the present invention, the temperature of the hydrothermal reaction is 120 to 200 ℃, wherein the temperature may be 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
Preferably, the hydrothermal reaction time is 5 to 7 hours, wherein the time may be 5 hours, 5.2 hours, 5.4 hours, 5.6 hours, 5.8 hours, 6.0 hours, 6.2 hours, 6.4 hours, 6.6 hours, 6.8 hours or 7 hours, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the hydrothermal reaction product is subjected to second cleaning by water and then is dried.
Preferably, the number of times of the second washing is equal to or greater than 2, wherein the number of times of the second washing may be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, etc., but is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
Preferably, the temperature of the drying is 50 to 100 ℃, wherein the temperature may be 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃ or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the drying time is 4-8 h, wherein the time can be 4h, 5h, 6h, 7h or 8h, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
As a preferable technical scheme of the invention, the phosphating treatment method is to carry out phosphating treatment on the precursor and sodium hypophosphite.
Preferably, the mass ratio of the precursor and the sodium hypophosphite is 1:5-1:30, wherein the mass ratio can be 1:5, 1:8, 1:10, 1:12, 1:14, 1:16, 1:18, 1:20, 1:22, 1:24, 1:26, 1:28 or 1:30, etc., but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the phosphating reaction gas comprises high purity PH 3 Gas, NH 4 HPO 2 Gas or NaHPO 2 Any one of the gases.
Preferably, the atmosphere of the phosphoric acid treatment is an inert atmosphere.
Preferably, the inert atmosphere comprises argon and/or nitrogen.
The phosphating reaction in the invention is a gas-solid phosphating reaction.
In a preferred embodiment of the present invention, the temperature of the phosphating reaction is 300 to 400 ℃, wherein the temperature may be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, or the like, but is not limited to the recited values, and other non-recited values within the range of the recited values are equally applicable.
Preferably, the phosphating reaction is performed for 30-180 min, wherein the time can be 30min, 40min, 50min, 60min, 70min, 80min, 90min, 100min, 110min, 120min, 130min, 140min, 150min, 160min, 170min or 180min, etc., but the present invention is not limited to the recited values, and other non-recited values within the range of the values are equally applicable.
As a preferable technical scheme of the invention, the preparation method comprises the following steps:
placing the acidified three-dimensional carbon matrix in a transition metal cation salt solution for hydrothermal reaction at 150-200 ℃ for 5-7 h, drying at 50-100 ℃ for 4-8 h to obtain a precursor, and performing phosphating treatment at 300-400 ℃ on the precursor for 30-90 min to obtain the dual-function current collector.
The second object of the invention is to provide a dual-function current collector, which is prepared by the preparation method according to one of the objects.
It is a further object of the present invention to provide a lithium sulfur battery comprising the dual-function current collector as defined in the second object.
Illustratively, the dual-function current collector in the present invention serves as a positive electrode sulfur carrier, and the positive electrode active material is sulfur.
Compared with the prior art, the invention has the following beneficial effects:
(1) The dual-function current collector prepared by the invention is a current collector subjected to matrix surface modification treatment, and the three-dimensional carbon material with high specific surface area is used for matrix surface modification, so that not only can the conductivity of a battery be effectively improved and the volume expansion of an electrode in the charge and discharge process be relieved, but also the current density of a negative electrode can be reduced to relieve the growth of lithium dendrites, the functions of sulfur fixation and lithium affinity of the current collector can be effectively considered, the dual-function current collector can be used on both sides of the positive electrode and the negative electrode of the battery, the positive electrode and the negative electrode can be simultaneously improved through the design and the preparation of the dual-function current collector, the utilization rate of positive electrode sulfur can be effectively improved and the conversion of LiPS can be accelerated when the dual-function current collector is applied to a lithium sulfur battery, the N/P ratio can be reduced, the stability of a lithium metal negative electrode can be improved, and the high energy density of the lithium sulfur battery can be realized;
(2) The preparation process of the dual-function current collector is simple, can be prepared in batches and has low preparation cost.
Drawings
FIG. 1 is Ni in example 1 of the present invention 2 And (3) preparing a P@CC dual-function current collector.
Fig. 2 is a graph showing comparison of coulombic efficiency of lithium deposition/exfoliation processes of example 1 and comparative example 1 of the present invention.
Fig. 3 is a graph showing cycle performance comparison of lithium sulfur half cells of example 1 and comparative example 1 of the present invention.
Fig. 4 is a topography on a current collector after 100 cycles of lithium deposition/stripping for example 1 and comparative example 1 of the present invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The present embodiment provides a Ni 2 The preparation method of the P@CC dual-function current collector is shown in a flow chart of the preparation method as shown in fig. 1, and comprises the following steps:
soaking commercial carbon cloth (CC for short) in a reaction kettle of a 3M nitric acid solution, screwing the reaction kettle, acidifying for 6 hours at 150 ℃, taking out the acidified commercial carbon cloth, and cleaning the commercial carbon cloth with deionized water until a cleaning solution is neutral to obtain the acidified commercial carbon cloth;
0.28g of nickel nitrate hexahydrate was dissolved in 40mL of methanol solution to give a nickel nitrate methoxide solution, which was added to the Teflon liner;
cutting acidified commercial carbon cloth into carbon cloth with the size of 3cm multiplied by 4cm, adding the carbon cloth into a nickel nitrate methanol solution, performing hydrothermal reaction at 180 ℃ for 6 hours, taking out the carbon cloth, washing twice with deionized water, and putting the carbon cloth into an oven at 80 ℃ for 6 hours to obtain nickel hydroxide nanosheet modified carbon cloth (Ni (OH) 2 @CC)。
Nickel hydroxide nano-sheet modified carbon cloth (Ni (OH)) with mass ratio of 1:12 2 @CC) and sodium hypophosphite are placed in a corundum boat, and are subjected to phosphating treatment for 1h at 350 ℃, and the reaction gas of the phosphating treatment is high-purity PH 3 The atmosphere is argon atmosphere, and Ni is obtained 2 P@CC dual-function current collector.
Example 2
The embodiment provides a preparation method of a CoP@CC dual-function current collector, which comprises the following steps:
soaking commercial carbon cloth in a reaction kettle of a 3M nitric acid solution, screwing the reaction kettle, acidifying for 6 hours at 150 ℃, taking out the acidified commercial carbon cloth, and cleaning the commercial carbon cloth with deionized water until a cleaning solution is neutral to obtain the acidified commercial carbon cloth;
0.291g of cobalt nitrate, 0.093g of ammonium fluoride and 0.3g of urea were dissolved in 20mL of deionized water to obtain a cobalt nitrate-ammonium fluoride-urea solution, which was added to a Teflon liner;
cutting acidified commercial carbon cloth into carbon cloth with the size of 2cm multiplied by 3cm, putting the carbon cloth into cobalt nitrate-ammonium fluoride-urea solution, performing hydrothermal reaction at 120 ℃ for 6 hours, taking out the carbon cloth, washing the carbon cloth twice with deionized water, putting the carbon cloth into an oven at 80 ℃ for 6 hours, and obtaining cobalt hydroxide nanosheet modified carbon cloth (Co (OH) 2 @CC)。
Cobalt hydroxide nanosheets with mass ratio of 1:5 are modified into carbon cloth (Co (OH) 2 @CC) and sodium hypophosphite are placed in a corundum boat, and are subjected to phosphating treatment for 1h at 400 ℃, and the reaction gas of the phosphating treatment is high-purity PH 3 The atmosphere is argon atmosphere, and the CoP@CC dual-function current collector is obtained.
Example 3
The present embodiment provides a Ni 2 The preparation method of the P@CP dual-function current collector comprises the following steps:
immersing carbon paper (carbon paper) in a 2M nitric acid solution reaction kettle, screwing the reaction kettle, acidifying for 6 hours at 150 ℃, taking out the acidified carbon paper, and washing the acidified carbon paper with deionized water until a washing liquid is neutral to obtain acidified carbon paper;
0.28g of nickel nitrate hexahydrate was dissolved in 40mL of methanol solution to give a nickel nitrate methoxide solution, which was added to the Teflon liner;
cutting acidified carbon paper into carbon paper with the size of 3cm multiplied by 4cm, putting the carbon paper into a nickel methoxide solution, performing hydrothermal reaction for 5 hours at 200 ℃, taking out the carbon paper, washing the carbon paper twice with deionized water, putting the carbon paper into an oven at 80 ℃ for 6 hours, and obtaining nickel hydroxide nanosheet modified carbon paper (Ni (OH) 2 @CP)。
Nickel hydroxide nanosheet modified carbon paper (Ni (OH)) with mass ratio of 1:30 2 At CP) and sodium hypophosphite are placed in a corundum boat, and phosphating is carried out for 90min at 300 ℃, and the reaction gas of the phosphating is high purityPH 3 The atmosphere is argon atmosphere, and Ni is obtained 2 P@CP dual-function current collector.
Example 4
This example was conducted under the same conditions as in example 1 except that the temperature of the phosphating reaction was changed to 300 ℃.
Example 5
This example was conducted under the same conditions as in example 1 except that the temperature of the phosphating reaction was changed to 450 ℃.
Comparative example 1
The comparative example uses commercial carbon cloth directly as a current collector.
Comparison of the coulombic efficiency of the battery lithium deposition/stripping process in example 1 and comparative example 1 as shown in fig. 2, the coulombic efficiency of the battery lithium deposition/stripping in example 1 was stabilized at 100% for 500 cycles; whereas comparative example 1 showed a fluctuation in coulomb efficiency in less than 100 cycles and a significant decrease after 300 cycles.
The cycle performance pairs of the lithium sulfur half-cell in example 1 and comparative example 1 are shown in FIG. 3, the maximum specific capacity of the cell in example 1 is 1100mAh/g, the capacity retention rate after 300 cycles is 92%, and the single-cycle attenuation rate is 0.026%; and the maximum capacity of the battery in comparative example 1 was 770mAh/g, the capacity retention after 300 cycles was 69.7%, and the single-turn attenuation was 0.101%.
The morphology of the lithium in example 1 and comparative example 1 on the current collector after 100 cycles of deposition/stripping is shown in fig. 4, the surface of the lithium metal in example 1 is flat and smooth, and the lithium metal in comparative example 1 is cracked and a large amount of dendrites grow.
Comparative example 2
Comparative example was not to Ni (OH) 2 Phosphating of @ CC, i.e. directly with Ni (OH) 2 Except that @ CC was used as the current collector, the other conditions were the same as in example 1.
Comparative example 3
The comparative example was conducted under the same conditions as in example 1 except that the three-dimensional carbon substrate was not subjected to the acidification treatment.
The current collectors prepared in examples 1 to 5 and comparative examples 1 to 3 were assembled into batteries, and the electrochemical properties of the batteries were tested, and the test results are shown in table 1.
The battery assembling method comprises the following steps: and (3) punching the current collector into a phi 12 wafer assembled battery by using a die, wherein the electrolyte is a conventional ether electrolyte system.
The testing method comprises the following steps:
1. test of deposition/stripping behavior: the lithium deposition/stripping behavior was tested with the current collectors prepared in examples 1-5 and comparative examples 1-3 as positive electrodes, lithium foil as negative electrode, assembled button cell, separator Celgard.
2. Test of catalytic performance of sulfur-containing active substances: the current collectors prepared in examples 1 to 5 and comparative examples 1 to 3 were used as positive electrodes, lithium foil was used as negative electrode, the separator was Celgard, and the electrolyte used on the positive electrode side contained dissolved Li 2 S 8 The electrolyte used on the negative electrode side is a conventional ether electrolyte, and the catalytic performance of the electrolyte on sulfur-containing active substances is tested.
3. Test of electrochemical performance of the dual-function current collector in full cell: the current collectors prepared in examples 1 to 5 and comparative examples 1 to 3 were used as positive electrodes by depositing a layer of metallic lithium on the surfaces of the current collectors prepared in examples 1 to 5 and comparative examples 1 to 3, and then taking out the current collectors as negative electrodes, and the electrolyte used on the positive electrode side contains dissolved Li 2 S 8 The electrolyte used on the negative electrode side is a conventional ether electrolyte, and the cycle performance of the dual-function current collector in a full battery at 0.5C is tested.
TABLE 1
The current collector can not only stabilize the stripping/depositing behavior of the lithium metal of the negative electrode, but also effectively improve the sulfur utilization rate and the sulfur fixing effect of the positive electrode due to the catalysis effect of the current collector, and has dual functions.
The applicant declares that the above is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that are easily conceivable within the technical scope of the present invention disclosed by the present invention fall within the scope of the present invention and the disclosure.
Claims (10)
1. The preparation method of the dual-function current collector is characterized by comprising the following steps of:
and placing the acidified three-dimensional carbon matrix in a transition metal cation salt solution for hydrothermal reaction, drying to obtain a precursor, and carrying out phosphating treatment on the precursor to obtain the dual-function current collector.
2. The method of claim 1, wherein the acidification is an acidification of the three-dimensional carbon matrix by immersing in an acidic solution;
preferably, the acidification is followed by a first wash with water until the wash is neutral;
preferably, the three-dimensional carbon matrix comprises any one of commercial carbon cloth, carbon paper, carbonized cotton cloth or coaxial spinning carbon film;
preferably, the acidic solution comprises a nitric acid solution;
preferably, the concentration of the nitric acid solution is 2-4M;
preferably, the acidification is carried out in a reaction kettle;
preferably, the acidification temperature is 140-160 ℃;
preferably, the acidification time is 5-7 hours.
3. The preparation method according to claim 1 or 2, wherein the solvent of the hydrothermal reaction comprises any one or a combination of at least two of water, methanol, ethanol or DMF;
preferably, the transition metal cation salt in the transition metal cation salt solution comprises any one or a combination of at least two of ferric nitrate, nickel nitrate, cobalt nitrate, ferric chloride, nickel sulfate or cobalt acetate.
4. A method of preparation according to any one of claims 1 to 3 wherein the temperature of the hydrothermal reaction is 120 to 200 ℃;
preferably, the hydrothermal reaction time is 5 to 7 hours.
5. The method according to any one of claims 1 to 4, wherein the second washing of the hydrothermal reaction product with water is followed by the drying;
preferably, the number of times of the second cleaning is more than or equal to 2;
preferably, the temperature of the drying is 50-100 ℃;
preferably, the drying time is 4-8 hours.
6. The method according to any one of claims 1 to 5, wherein the phosphating is carried out by phosphating a precursor with sodium hypophosphite;
preferably, the mass ratio of the precursor to the sodium hypophosphite is 1:5-1:30;
preferably, the phosphating reaction gas comprises high purity PH 3 Gas, NH 4 HPO 2 Gas or NaHPO 2 Any one of the gases;
preferably, the atmosphere of the phosphoric acid treatment is an inert atmosphere;
preferably, the inert atmosphere comprises argon and/or nitrogen.
7. The method of any one of claims 1-6, wherein the temperature of the phosphating reaction is 300-400 ℃;
preferably, the phosphating reaction time is 30-180 min.
8. The method of any one of claims 1-7, wherein the method of preparation comprises:
placing the acidified three-dimensional carbon matrix in a transition metal cation salt solution for hydrothermal reaction at 150-200 ℃ for 5-7 h, drying at 50-100 ℃ for 4-8 h to obtain a precursor, and performing phosphating treatment at 300-400 ℃ on the precursor for 30-90 min to obtain the dual-function current collector.
9. A dual-function current collector prepared by the preparation method according to any one of claims 1 to 8.
10. A lithium sulfur battery comprising the dual function current collector of claim 9.
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