CN113036113A - Doped BaSO4Sodium ion battery cathode material and preparation method thereof - Google Patents
Doped BaSO4Sodium ion battery cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN113036113A CN113036113A CN202110267775.5A CN202110267775A CN113036113A CN 113036113 A CN113036113 A CN 113036113A CN 202110267775 A CN202110267775 A CN 202110267775A CN 113036113 A CN113036113 A CN 113036113A
- Authority
- CN
- China
- Prior art keywords
- sno
- baso
- zns
- composite material
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000010406 cathode material Substances 0.000 title abstract description 17
- 239000002131 composite material Substances 0.000 claims abstract description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 82
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 53
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 52
- 239000000463 material Substances 0.000 claims abstract description 48
- 239000002243 precursor Substances 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000003756 stirring Methods 0.000 claims abstract description 31
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007773 negative electrode material Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 150000003751 zinc Chemical class 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 81
- 239000012153 distilled water Substances 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 238000001035 drying Methods 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 30
- 238000000498 ball milling Methods 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 18
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 17
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 17
- 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 10
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 10
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 239000011734 sodium Substances 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
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 239000002244 precipitate Substances 0.000 claims description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 6
- 239000008103 glucose Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims description 3
- 229920002472 Starch Polymers 0.000 claims description 3
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 239000001119 stannous chloride Substances 0.000 claims description 3
- 235000011150 stannous chloride Nutrition 0.000 claims description 3
- 239000008107 starch Substances 0.000 claims description 3
- 235000019698 starch Nutrition 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- 239000004246 zinc acetate Substances 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000007772 electrode material Substances 0.000 abstract description 5
- 238000004146 energy storage Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 117
- 239000000843 powder Substances 0.000 description 33
- 238000007599 discharging Methods 0.000 description 22
- 229960001031 glucose Drugs 0.000 description 17
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 14
- 230000001376 precipitating effect Effects 0.000 description 13
- 238000001354 calcination Methods 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 8
- 239000011701 zinc Substances 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229920001410 Microfiber Polymers 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 7
- 239000006230 acetylene black Substances 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 239000013543 active substance Substances 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000011889 copper foil Substances 0.000 description 7
- 238000005520 cutting process Methods 0.000 description 7
- 238000009837 dry grinding Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- 239000012528 membrane Substances 0.000 description 7
- 239000003658 microfiber Substances 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 7
- BAZAXWOYCMUHIX-UHFFFAOYSA-M sodium perchlorate Chemical compound [Na+].[O-]Cl(=O)(=O)=O BAZAXWOYCMUHIX-UHFFFAOYSA-M 0.000 description 7
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 7
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 238000000227 grinding Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910014573 C—SnO2 Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229940079101 sodium sulfide Drugs 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000013332 literature search Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a doped BaSO4The negative electrode material of the sodium-ion battery and the preparation method thereof comprise the following steps: (1) one-step hydrothermal method for preparing SnO2A material; (2) SnO2Dissolving the material in deionized water, adding dilute sulfuric acid solution and Ba (OH)2Solution to realize BaSO4Doped SnO2A composite material; (3) the preparation of ZnS/C composite material by a carbothermic method comprises the following steps: dissolving zinc salt and a sulfur source serving as raw materials in deionized water, reacting to obtain a ZnS material precursor, dissolving the ZnS material precursor in the deionized water, adding an organic carbon source, stirring until all water is evaporated, and roasting in an inert atmosphere; (4) mixing BaSO4Doped SnO2The composite material and the ZnS/C composite material are mixed in proportion. BaSO doped by the method of the invention4The prepared electrode material can meet the performance requirements of the sodium ion battery cathode material, has higher initial capacity, better specific capacity, higher first coulombic efficiency and ideal cycle stability, and ensures that the sodium ion battery is in an energy storage systemThe position of the device is improved.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to a doped BaSO4The negative electrode material of the sodium ion battery and the preparation method thereof.
Background
The secondary battery technology is used as an important means for energy storage and conversion, and has very wide application in the fields of people's daily life, industrial production, military and national defense, aerospace and the like, so that the secondary battery occupies a vital position in the field of new energy. Currently, the lithium ion battery which is developed fastest and has the mature technology in the secondary battery system is receiving wide attention. However, the lithium resource in the earth's crust is very limited, and the consumption of the lithium resource is increasing year by year, which not only stimulates the continuous increase of the lithium price, but also raises the concern of the lithium reserves. Sodium ions and lithium ions have similar physicochemical properties, and a rocking chair type battery theoretical model suitable for lithium ion batteries is also suitable for sodium ion batteries. Compared with lithium ion batteries, sodium ion batteries have natural advantages in resource reserves and cost, and particularly in large-scale energy storage power stations, the use of sodium ion batteries can greatly relieve the pressure caused by lithium resource shortage, so that low-cost sodium ion batteries have great potential in future large-scale energy storage systems.
The negative electrode material of the sodium-ion battery is responsible for providing low oxidation-reduction potential and has high requirements on safety and effectiveness. The negative electrode material of the sodium ion battery is an important part of research, wherein the zinc-based material has better capacity retention, but the electrochemical property is not good enough, and the preparation of the composite material with the carbonaceous material is proposed to solve the problems. Tin dioxide is widely concerned due to the fact that tin dioxide has high specific capacity, large volume change exists in the charging and discharging process, collapse and breakage of materials are not caused, and the structure of the materials is basically kept intact. This finding demonstrates that tin dioxide theoretically has good cycling stability as a sodium ion battery negative electrode material. However, the cycle performance and rate capability of the current sodium-ion battery negative electrode material are still insufficient as can be seen from literature search.
Disclosure of Invention
In order to solve the above problems in the prior art, the present invention provides a doped BaSO4The negative electrode material of the sodium ion battery and the preparation method thereof are provided, namely SnO2Adding a trace amount of BaSO into the material4The electrochemical performance of the sodium ion battery cathode material is not influenced, the doping effect can be achieved, the initial capacity and the cycling stability of the battery are further improved, and the sodium ion battery cathode material with good performance is prepared at low cost.
The technical means adopted by the invention are as follows:
doped BaSO4The preparation method of the negative electrode material of the sodium-ion battery comprises the following preparation steps:
(1) one-step hydrothermal method for preparing SnO2Materials: carrying out hydrothermal reaction by taking a tin source, a dispersing agent and NaOH as raw materials, wherein the molar ratio of the tin source to the NaOH is 1: 10-15, the volume ratio of the dispersing agent to the NaOH is 1: 1-1.5, after the reaction is finished, centrifugally washing, collecting precipitate, and drying to obtain SnO2A material precursor;
(2) SnO2Dissolving the material precursor in deionized water, slowly adding dilute sulfuric acid solution and Ba (OH)2Magnetically stirring the solution at room temperature for 1-3 h;
(3) centrifugally washing the solution obtained in the step (2), collecting the precipitate, drying to obtain a composite material precursor, and roasting the composite material precursor in an air atmosphere to obtain BaSO4Doped SnO2A composite material;
(4) the preparation of ZnS/C composite material by a carbothermic method comprises the following steps: dissolving zinc salt and a sulfur source serving as raw materials in deionized water according to a molar ratio of 1: 1-2, transferring the solution to a reaction kettle, centrifugally washing after the reaction is finished, collecting precipitate, drying to obtain a ZnS material precursor, dissolving the ZnS material precursor in deionized water, adding an organic carbon source, magnetically stirring at 80 ℃ until all water is evaporated, and roasting in an inert atmosphere to obtain a ZnS/C composite material; the mass ratio of the ZnS material precursor to the organic carbon source is 1-3: 1;
(5) mixing BaSO4Doped SnO2The composite material and the ZnS/C composite material are mixed to prepare the ZnS/C-SnO material of the cathode of the sodium-ion battery2-BaSO4。
Further, in the step (1), the tin source is one or more of stannous chloride, stannic chloride and sodium thiostannate; the dispersing agent is one or more of PEG-400, PVP and DMF; the concentration of NaOH is 1-2 mol/L; dissolving a tin source, a dispersing agent and NaOH in deionized water, transferring the solution to a hydrothermal reaction kettle, and carrying out sealed reaction at the hydrothermal reaction temperature of 120-200 ℃ for 10-24 hours.
Further, the washing is carried out for more than 3 times by respectively adopting distilled water and absolute ethyl alcohol, and the drying is carried out for 10-12 h at the temperature of 60-80 ℃.
Further, in the step (2), Ba (OH)2The volume ratio of the solution to the dilute sulfuric acid solution is 3-6: 10-20, Ba (OH)2The concentration of the solution is 0.5-1 mol/L, and the concentration of the dilute sulfuric acid solution is 0.5 mol/L; SnO2The ratio of the material precursor to the deionized water is 1g: 10-30 ml.
Further, in the step (3), roasting is carried out for 2-6 h at 300-600 ℃ at a temperature rise rate of 5 ℃/min; generated BaSO4With SnO2The mass ratio of (A) to (B) is 1-10: 100.
Further, in the step (4), the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride; the sulfur source is one or more of thioacetamide, sodium sulfide and thiourea; the organic carbon source is one or more of glucose, citric acid, starch and polydopamine.
Further, in the step (4), the reaction temperature is 120-200 ℃, and the reaction time is 10-24 hours; the roasting is carried out for 2-6 h at the temperature of 600-900 ℃.
Further, in the step (5), the mixture is mixed by adopting a dry ball milling method, and BaSO4Doped SnO2The mass ratio of the composite material to the ZnS/C composite material is 1: 1-4; the ball-material ratio in the dry ball milling mode is 10-40: 1, the rotating speed is 200-1000 r/min, and the ball milling time is 1-10 h.
The invention also provides a BaSO-doped BaSO prepared by the preparation method4The negative electrode material of the sodium ion battery.
Compared with the prior art, the invention has the following advantages:
(1) doping with BaSO by adding barium salts and sulfate radicals4ZnS/C-SnO of2-BaSO4The negative electrode material of the sodium ion battery.
(2) The negative electrode ZnS/C-SnO of the sodium ion battery prepared by the method2-BaSO4Has better specific capacity, cycling stability and rate capability. At SnO2Adding a trace amount of BaSO into the material4The electrochemical performance of the cathode material of the sodium ion battery is not influenced, the doping effect can be achieved, and the initial capacity and the cycling stability of the battery are further improved.
(3) The invention prepares ZnS/C-SnO by a high-energy mechanical ball milling method2-BaSO4The cathode material has simple process and low preparation cost, and can be commercially produced.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows comparative example 1 ZnS/C-SnO2The sodium ion negative electrode battery prepared from the composite material has a current density of 50 mA.g-1Cycle performance and coulombic efficiency curves.
FIG. 2 shows example 13% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has a current density of 50 mA.g-1Cycle performance and coulombic efficiency curves.
FIG. 3 shows example 25% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has a current density of 50 mA.g-1Multiplying power cycle performance and coulombic efficiency curve.
FIG. 4 shows example 38% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has a current density of 50 mA.g-1Cycle performance and coulombic efficiency curves.
FIG. 5 shows example 410% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has a current density of 50 mA.g-1Multiplying power cycle performance and coulombic efficiency curve.
FIG. 6 shows example 55% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has the current density of 200 mA-g-1The following charge and discharge curves.
FIG. 7 shows example 65% BaSO4Doped ZnS/C-SnO2-BaSO4The sodium ion negative electrode battery prepared from the composite material has the current density of 200 mA-g-1The following charge and discharge curves.
Detailed Description
The technical solution of the present invention is further described below with reference to the accompanying drawings and specific examples, but the present invention is not limited to the following examples. The method is a conventional method unless otherwise specified. The starting materials are commercially available from the open literature unless otherwise specified.
The invention adopts the combination of a hydrothermal method, a carbothermic method, a calcining method and a mechanical ball milling method: SnO with uniform particles is prepared by a hydrothermal method2And ZnS, further performing carbothermic reduction, calcination and ball milling to obtain a negative electrode material ZnS/C-SnO of the sodium-ion battery2-BaSO4. The cathode material is used for manufacturing a battery cathode to enable a sodium ion batteryExcellent charge-discharge specific capacity and ideal cycling stability can be obtained.
The invention provides a doped BaSO4The sodium ion battery negative electrode material and the preparation method thereof comprise the following preparation steps:
(1) one-step hydrothermal method for preparing SnO2Materials: carrying out hydrothermal reaction by taking a tin source, a dispersing agent and NaOH as raw materials, wherein the molar ratio of the tin source to the NaOH is 1: 10-15, the volume ratio of the dispersing agent to the NaOH is 1: 1-1.5, after the reaction is finished, centrifugally washing, collecting precipitate, and drying to obtain SnO2A material precursor;
the tin source is one or more of stannous chloride, stannic chloride and sodium thiostannate; the dispersing agent is one or more of PEG-400, PVP and DMF; the concentration of NaOH is 1-2 mol/L; the hydrothermal reaction temperature is 120-200 ℃, and the reaction time is 10-24 h.
(2) SnO2Dissolving the material precursor in deionized water, slowly adding dilute sulfuric acid solution and Ba (OH)2Magnetically stirring the solution at room temperature for 1-3 h;
Ba(OH)2the volume ratio of the solution to the dilute sulfuric acid solution is 3-6: 10-20, Ba (OH)2The concentration of the solution is 0.5-1 mol/L, and the concentration of the dilute sulfuric acid solution is 0.5 mol/L; SnO2The ratio of the material precursor to the deionized water is 1g: 10-30 ml.
(3) Centrifugally washing the solution obtained in the step (2), collecting precipitates, drying to obtain a composite material precursor, placing the composite material precursor in an air atmosphere, and roasting at 300-600 ℃ for 2-6 h at a heating rate of 5 ℃/min to obtain BaSO4Doped SnO2A composite material; generated BaSO4With SnO2The mass ratio of (A) to (B) is 1-10: 100.
(4) The preparation of ZnS/C composite material by a carbothermic method comprises the following steps: dissolving zinc salt and a sulfur source serving as raw materials in deionized water according to a molar ratio of 1: 1-2, transferring the solution to a reaction kettle, centrifugally washing after the reaction is finished, collecting precipitate, drying to obtain a ZnS material precursor, dissolving the ZnS material precursor in deionized water, adding an organic carbon source, magnetically stirring at 80 ℃ until all water is evaporated, and roasting at 600-900 ℃ for 2-6 hours in an inert atmosphere to obtain a ZnS/C composite material; the mass ratio of the ZnS material precursor to the organic carbon source is 1-3: 1;
the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride; the sulfur source is one or more of thioacetamide, sodium sulfide and thiourea; the organic carbon source is one or more of glucose, citric acid, starch and polydopamine; the reaction temperature is 120-200 ℃, and the reaction time is 10-24 h.
(5) Mixing BaSO4Doped SnO2The composite material and the ZnS/C composite material are mixed by adopting a dry ball milling way to prepare the ZnS/C-SnO negative electrode material of the sodium-ion battery2-BaSO4；BaSO4Doped SnO2The mass ratio of the composite material to the ZnS/C composite material is 1: 1-4; the ball-material ratio in the dry ball milling mode is 10-40: 1, the rotating speed is 200-1000 r/min, and the ball milling time is 1-10 h.
The washing is carried out for more than 3 times by respectively adopting distilled water and absolute ethyl alcohol, and the drying is carried out for 10-12 h at the temperature of 60-80 ℃.
Comparative example 1
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor. Calcining the mixture for 2 hours at 500 ℃ in air atmosphere to obtain pure SnO2And (3) powder.
② zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose are taken as raw materials, 3.23g of C is weighed according to the molar ratio of 1:24H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and anhydrous glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, calcining the solution for 2h at 750 ℃ in a nitrogen atmosphere to obtain the active glucose-based catalystZnS/C composite material.
Thirdly, SnO is subjected to dry grinding by adopting a mechanical ball milling mode2Mixing the material and ZnS/C composite material according to the mass ratio of 1:3, ball-milling for 5 hours at the speed of 200r/min with the ball-material ratio of 20:1 to prepare 0 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2。
ZnS/C-SnO prepared by the comparative example2The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3V. The cycling performance and coulombic efficiency curves of the cells were tested and the results are shown in fig. 1. From this it can be seen that ZnS/C-SnO2Composite material 50mA g-1The charging and discharging specific capacity of the constant-current circulation curve is gradually reduced along with the increase of the circulation in the first 30 times of circulation, and the charging and discharging specific capacity of the material slowly attenuates along with the circulation times in the last 20 times of circulation. At 50mA · g-1Under the current density, the charging and discharging specific capacity after 50 times of circulation is 151.7mAh g-1/156mAh·g-1. It can be seen that the undoped BaSO4ZnS/C-SnO of2The cycle performance of the composite material is poor.
Example 1
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, to which 5ml of 0.5mol/L Ba (OH) was added under magnetic stirring2Magnetically stirring the prepared solution and 7.5ml of 0.5mol/L dilute sulfuric acid solution at room temperature for 1h, washing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying box, preserving heat at 60 ℃ for 12h, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, preserving heat at 500 ℃ for 2h at the heating rate of 5 ℃/min, and cooling the furnace to room temperature after the reaction is finished to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and anhydrous glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, and calcining the solution for 2h at 750 ℃ in a nitrogen atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:3, ball-milling for 5 hours at the ball-material ratio of 20:1 and200 r/min to prepare 3 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
The 3% BaSO obtained in this example was added4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber Membrane, model numberAnd assembling the button half-cell into a CR2025 type button half-cell in an argon-filled glove box for GF/D.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3V. The cycling performance and coulombic efficiency curves of the cells were tested and the results are shown in fig. 2. From this it can be seen that 3% BaSO4Doped ZnS/C-SnO2-BaSO4Composite material 50mA g-1The first charge-discharge specific capacity of the constant-current circulation curve is 433.3 mAh.g-1/717.4mAh·g-1The first coulombic efficiency is 60.4 percent, and the charging and discharging specific capacity is 186.3 mAh.g after 50 cycles-1/190.3mAh·g-1The cycle efficiency was 97.8%. It can be seen that 3% BaSO is compared with comparative example 14The cycle performance of the doped composite material is improved.
Example 2
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, to which was added 3.5ml of 0.5mol/L Ba (OH) under magnetic stirring2Magnetically stirring the prepared solution and 10ml of 0.5mol/L dilute sulfuric acid solution at room temperature for 1h, washing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying box, keeping the temperature at 60 ℃ for 12h, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, keeping the temperature at 500 ℃ for 2h at the heating rate of 5 ℃/min, and cooling the furnace to room temperature after the reaction is finished to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2O is dissolved in 150m in turnL distilled water forms clear transparent solution, the clear transparent solution is moved into a reaction kettle to carry out hydrothermal reaction for 12 hours at 180 ℃, the reaction kettle is washed and precipitated for three times by distilled water and absolute ethyl alcohol respectively, the reaction kettle is dried for 12 hours at 60 ℃ to obtain precursor powder, the precursor powder and absolute glucose are dissolved in deionized water according to the mass ratio of 1:1, the mixture is stirred in water bath at 80 ℃ until water is evaporated, and the mixture is calcined for 2 hours at 750 ℃ in nitrogen atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:3, ball-milling for 5 hours at the ball-material ratio of 20:1 and200 r/min to prepare 5 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
5% BaSO obtained in this example4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3V. The rate capability and coulombic efficiency curves of the cell were tested and the results are shown in figure 3. Thus, ZnS/C-SnO2-BaSO4The charging and discharging specific capacity of the composite material is gradually reduced in a step manner along with the change of the current density, and when the current density is reduced to 0.05 A.g again-1And the charging and discharging specific capacity is obviously increased, which shows that the composite material has good capacity recovery. As can be seen from FIG. 3, ZnS/C-SnO was observed at various current densities2-BaSO4The composite material has good specific capacity which is 0.05 A.g for the first time-1The charging and discharging specific capacity under the current density is 474.3mAh g-1/761.9mAh·g-1. When the current density is restored to 0.05A · g again-1The specific charge-discharge capacity still remains 416.4 mAh.g-1/436mAh·g-1After the circulation is continued for 20 times, the charging and discharging specific capacity is still maintained at 336.8mAh g-1/345.1mAh·g-1. As can be seen, the ZnS/C-SnO obtained in this example2-BaSO4The composite material shows very good capacity recovery and retention, which is one of the most important performance indexes for measuring electrode materials.
Example 3
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, to which 5ml of 0.5mol/L Ba (OH) was added under magnetic stirring2Magnetically stirring the prepared solution and 17.5ml of 0.5mol/L dilute sulfuric acid solution at room temperature for 1h, washing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying box, preserving heat at 60 ℃ for 12h, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, preserving heat at 500 ℃ for 2h at the heating rate of 5 ℃/min, and cooling the furnace to room temperature after the reaction is finished to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and absolute glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, and dissolving the solution in nitrogenCalcining for 2h at 750 ℃ in a gas atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:3, ball-milling for 5 hours at the speed of 200r/min with the ball-material ratio of 20:1 to prepare 8 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
The 8% BaSO obtained in this example was added4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3V. The cycling performance and coulombic efficiency curves of the cells were tested and the results are shown in fig. 4. From this it can be seen that ZnS/C-SnO2-BaSO4Composite material 50mA g-1The charging and discharging specific capacity of the constant-current circulation curve is gradually reduced along with the increase of the circulation in the first 5 times of circulation, and the charging and discharging specific capacity of the material slowly attenuates along with the circulation times in the last 20 times of circulation. At 50mA · g-1Under the current density, the charging and discharging specific capacity after 50 times of circulation is 212.3 mAh.g-1/212.7mAh·g-1. Thus, BaSO4The cycle performance of the alloy is obviously improved by doping.
Example 4
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. The solution is stirred evenly and transferred into a reaction kettle for hydrothermal reaction at 160 DEG CAfter reacting for 15h, washing and precipitating for three times by distilled water and absolute ethyl alcohol respectively, and drying for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, and 4.5ml of 0.5mol/L Ba (OH) was added thereto under magnetic stirring2Magnetically stirring the prepared solution and20 ml of 0.5mol/L dilute sulfuric acid solution at room temperature for 1h, washing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying box, keeping the temperature at 60 ℃ for 12h, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, keeping the temperature at 500 ℃ for 2h at the heating rate of 5 ℃/min, and cooling the furnace to room temperature after the reaction is finished to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and anhydrous glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, and calcining the solution for 2h at 750 ℃ in a nitrogen atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:3, ball-milling for 5 hours at the speed of 200r/min with the ball-material ratio of 20:1 to prepare 10 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
The 10% BaSO obtained in this example was added4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Using pure sodium sheet as counter electrode and sodium perchlorate as electrolyte solution (NC-008) with a formulation of 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-3V. The rate capability and coulombic efficiency curves of the cell were tested and the results are shown in figure 5. Thus, ZnS/C-SnO2-BaSO4The charging and discharging specific capacity of the composite material is gradually reduced in a step manner along with the change of the current density, and when the current density is reduced to 0.05 A.g again-1And the charging and discharging specific capacity is obviously increased, which shows that the composite material has good capacity recovery. As can be seen from FIG. 5, ZnS/C-SnO was observed at various current densities2-BaSO4The composite material has good specific capacity which is 0.05 A.g for the first time-1The charge-discharge specific capacity under the current density is 536.3 mAh.g-1/979.7mAh·g-1. When the current density is recovered to 0.05 A.g-1The charging and discharging specific capacity is still maintained at 301.8mAh g after the continuous circulation for 20 times-1/309.2mAh·g-1。
As can be seen, the ZnS/C-SnO obtained in this example2-BaSO4The composite material shows very good capacity recovery and retention, which is one of the most important performance indexes for measuring electrode materials.
Example 5
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, to which was added 3.5ml of 0.5mol/L Ba (OH) under magnetic stirring2The prepared solution and 10ml of 0.5mol/L dilute sulfuric acid solution are magnetically stirred for 1 hour at room temperatureWashing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying oven, keeping the temperature for 12h at 60 ℃, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, keeping the temperature for 2h at 500 ℃ at the heating rate of 5 ℃/min, and cooling the furnace to room temperature after the reaction is finished to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and anhydrous glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, and calcining the solution for 2h at 750 ℃ in a nitrogen atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:1, ball-milling for 5 hours at the ball-material ratio of 20:1 and200 r/min to prepare 5 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
5% BaSO obtained in this example4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-2.5V. TestingThe charge and discharge performance of the cell was evaluated, and the results are shown in FIG. 6 as ZnS/C-SnO2-BaSO4The composite material is at 200 mA.g-1Constant current charge and discharge curves for the first 5 times at current density. As the 2 nd to 5 th charging curves are almost overlapped, the electrode material has little discharge specific capacity attenuation, and the first charge-discharge specific capacity of the material is 378.9 mAh.g-1/668.4mAh·g-1The first coulombic efficiency is 56.7%, and the charge-discharge specific capacity is good.
Example 6
Taking crystallized stannic chloride, N-dimethylformamide and sodium hydroxide as raw materials, and weighing 2mmol of SnCl4·5H2O and 10ml of DMF were dissolved in 10ml of distilled water, and 10ml of a 2mol/L NaOH solution was added dropwise with stirring. Uniformly stirring the solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 15h at 160 ℃, washing and precipitating the solution for three times by using distilled water and absolute ethyl alcohol respectively, and drying the solution for 12h at 60 ℃ to obtain white SnO2And (3) precursor.
② taking 5g SnO2The powder was dissolved in 50ml of deionized water, to which was added 3.5ml of 0.5mol/L Ba (OH) under magnetic stirring2Magnetically stirring the prepared solution and 10ml of 0.5mol/L dilute sulfuric acid solution at room temperature for 1h, washing the obtained solution with distilled water and absolute ethyl alcohol for three times to realize solid-liquid separation, placing the solution in a drying box, preserving heat for 12h at 60 ℃, grinding the dried solid into uniform powder, placing the powder in a muffle furnace, preserving heat for 2h at 500 ℃ at the heating rate of 5 ℃/min to obtain BaSO4Doped SnO2A composite material.
③ 3.23g of C is weighed according to the molar ratio of 1:2 by using zinc acetate dihydrate, sodium sulfide nonahydrate and anhydrous glucose as raw materials4H6O4Zn·2H2O and 5.654g of Na2S·9H2Dissolving O in 150mL of distilled water in sequence to form a clear transparent solution, transferring the solution into a reaction kettle, carrying out hydrothermal reaction for 12h at 180 ℃, washing and precipitating the solution three times by using distilled water and absolute ethyl alcohol respectively, drying the solution for 12h at 60 ℃ to obtain precursor powder, dissolving the precursor powder and anhydrous glucose in deionized water according to the mass ratio of 1:1, stirring the solution in a water bath at 80 ℃ until water is evaporated, and calcining the solution for 2h at 750 ℃ in a nitrogen atmosphere to obtain the ZnS/C composite material.
Fourthly, adopting a mechanical ball milling dry grinding mode to carry out BaSO4Doped SnO2Mixing the composite material and the ZnS/C composite material according to the mass ratio of 1:2, ball-milling for 5 hours at the ball-material ratio of 20:1 and200 r/min to prepare 5 percent BaSO4Doped sodium ion battery cathode material ZnS/C-SnO2-BaSO4。
5% BaSO obtained in this example4Doped ZnS/C-SnO2-BaSO4The composite material is used as an active material of a negative electrode of a sodium ion battery, and is mixed with acetylene black and a binder PVDF/NMP according to a mass ratio of 70: 20: 10 to prepare slurry, and then coating the slurry on a copper foil to form a film. Vacuum drying at 80 deg.C for 12 hr, cutting into pieces and tabletting, wherein the weight of active substance in the electrode slice is about 2 mg. Pure sodium sheet is taken as a counter electrode, sodium perchlorate is taken as electrolyte (NC-008), and the formula is 1.0 mol.L-1NaClO4(EC: EDC 1:1 Vol% with 5% FEC), Whatman glass microfiber membrane, model GF/D, assembled into CR2025 button half-cell in argon filled glove box.
In the experiment, a battery performance tester LAND2001CT is used for carrying out charging and discharging and cycle performance tests, and the voltage range is 0.01-2.5V. The cell was tested for charge and discharge performance and the results are shown in FIG. 7 as ZnS/C-SnO2-BaSO4The composite material is at 200 mA.g-1Constant current charge and discharge curves for the first 5 times at current density. As the 2 nd to 5 th charging curves are almost overlapped, the electrode material has little discharge specific capacity attenuation, and the first charge-discharge specific capacity of the material is 454.7 mAh.g-1/760.7mAh·g-1The first coulombic efficiency is 59.8%, and the charge-discharge specific capacity is good.
As proved by the above examples and test results, the doped BaSO prepared by the method of the invention4The prepared sodium ion battery cathode material can meet the performance requirements of the sodium ion battery cathode material, has higher initial capacity, better specific capacity, higher first coulombic efficiency and ideal cycle stability, and improves the position of the sodium ion battery in an energy storage system.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. Doped BaSO4The preparation method of the negative electrode material of the sodium-ion battery is characterized by comprising the following preparation steps:
(1) one-step hydrothermal method for preparing SnO2Materials: carrying out hydrothermal reaction by taking a tin source, a dispersing agent and NaOH as raw materials, wherein the molar ratio of the tin source to the NaOH is 1: 10-15, the volume ratio of the dispersing agent to the NaOH is 1: 1-1.5, after the reaction is finished, centrifugally washing, collecting precipitate, and drying to obtain SnO2A material precursor;
(2) SnO2Dissolving the material precursor in deionized water, slowly adding dilute sulfuric acid solution and Ba (OH)2Magnetically stirring the solution at room temperature for 1-3 h;
(3) centrifugally washing the solution obtained in the step (2), collecting the precipitate, drying to obtain a composite material precursor, and roasting the composite material precursor in an air atmosphere to obtain BaSO4Doped SnO2A composite material;
(4) the preparation of ZnS/C composite material by a carbothermic method comprises the following steps: dissolving zinc salt and a sulfur source serving as raw materials in deionized water according to a molar ratio of 1: 1-2, transferring the solution to a reaction kettle, centrifugally washing and collecting precipitates after reaction is finished, drying to obtain a ZnS material precursor, dissolving the ZnS material precursor in deionized water, adding an organic carbon source, magnetically stirring at 80 ℃ until all water is evaporated, and roasting in an inert atmosphere to obtain a ZnS/C composite material, wherein the mass ratio of the ZnS material precursor to the organic carbon source is 1-3: 1;
(5) mixing BaSO4Doped SnO2The composite material and the ZnS/C composite material are mixed to prepare the ZnS/C-SnO material of the cathode of the sodium-ion battery2-BaSO4。
2. The preparation method according to claim 1, wherein in the step (1), the tin source is one or more of stannous chloride, stannic chloride and sodium thiostannate; the dispersing agent is one or more of PEG-400, PVP and DMF; the concentration of the NaOH is 1-2 mol/L; the hydrothermal reaction temperature is 120-200 ℃, and the reaction time is 10-24 h.
3. The method according to claim 1, wherein the washing is performed 3 or more times by using distilled water and absolute ethyl alcohol, and the drying is performed at 60 to 80 ℃ for 10 to 12 hours.
4. The method according to claim 1, wherein in the step (2), Ba (OH)2The volume ratio of the solution to the dilute sulfuric acid solution is 3-6: 10-20; said Ba (OH)2The concentration of the solution is 0.5-1 mol/L, and the concentration of the dilute sulfuric acid solution is 0.5 mol/L; the SnO2The ratio of the material precursor to the deionized water is 1g: 10-30 ml.
5. The preparation method according to claim 1, wherein in the step (3), the roasting is carried out at 300-600 ℃ for 2-6 h at a temperature rise rate of 5 ℃/min; generated BaSO4With SnO2The mass ratio of (A) to (B) is 1-10: 100.
6. The preparation method according to claim 1, wherein in the step (4), the zinc salt is one or more of zinc acetate, zinc nitrate and zinc chloride; the sulfur source is one or more of thioacetamide, sodium sulfide and thiourea; the organic carbon source is one or more of glucose, citric acid, starch and polydopamine.
7. The preparation method according to claim 1, wherein in the step (4), the reaction temperature is 120-200 ℃, and the reaction time is 10-24 h; the roasting is carried out for 2-6 h at the temperature of 600-900 ℃.
8. The method according to claim 1, wherein in the step (5), the mixing is performed by dry ball milling, and the BaSO is added4Doped SnO2The mass ratio of the composite material to the ZnS/C composite material is 1: 1-4; the ball-material ratio in the dry ball milling mode is 10-40: 1, the rotating speed is 200-1000 r/min, and the ball milling time is 1-10 h.
9. The negative electrode material of the sodium-ion battery obtained by the preparation method according to any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110267775.5A CN113036113B (en) | 2021-03-11 | 2021-03-11 | Doped BaSO4Sodium ion battery cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110267775.5A CN113036113B (en) | 2021-03-11 | 2021-03-11 | Doped BaSO4Sodium ion battery cathode material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113036113A true CN113036113A (en) | 2021-06-25 |
| CN113036113B CN113036113B (en) | 2022-06-03 |
Family
ID=76469880
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110267775.5A Expired - Fee Related CN113036113B (en) | 2021-03-11 | 2021-03-11 | Doped BaSO4Sodium ion battery cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113036113B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680374A (en) * | 2021-09-28 | 2021-11-23 | 中化学朗正环保科技有限公司 | Composite photocatalyst and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| JP2015197976A (en) * | 2014-03-31 | 2015-11-09 | 株式会社日本触媒 | Mixture for zinc electrode |
| CN105514392A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | SnS2-SnO2 nanometer flake-shaped sodium ion battery cathode material and preparation method thereof |
| CN105552351A (en) * | 2016-01-25 | 2016-05-04 | 陕西科技大学 | Nano-particle-assembled spherical SnO2 sodium-ion battery cathode material and preparation method thereof |
| CN108767240A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN109378458A (en) * | 2018-10-22 | 2019-02-22 | 东北大学 | It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method |
| CN110534727A (en) * | 2019-08-06 | 2019-12-03 | 中南大学 | A kind of tin zinc double metallic composite material and preparation method thereof |
| CN111017988A (en) * | 2019-12-31 | 2020-04-17 | 深圳爱多科传感技术有限公司 | Formaldehyde gas-sensitive material based on recovery treatment of tin mud and preparation method thereof |
-
2021
- 2021-03-11 CN CN202110267775.5A patent/CN113036113B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738077A (en) * | 2005-09-06 | 2006-02-22 | 天津力神电池股份有限公司 | Method for preparing negative pole material of lithium ion cell high-capacity tin composite |
| JP2015197976A (en) * | 2014-03-31 | 2015-11-09 | 株式会社日本触媒 | Mixture for zinc electrode |
| CN105514392A (en) * | 2016-01-25 | 2016-04-20 | 陕西科技大学 | SnS2-SnO2 nanometer flake-shaped sodium ion battery cathode material and preparation method thereof |
| CN105552351A (en) * | 2016-01-25 | 2016-05-04 | 陕西科技大学 | Nano-particle-assembled spherical SnO2 sodium-ion battery cathode material and preparation method thereof |
| CN108767240A (en) * | 2018-06-11 | 2018-11-06 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of lithium ion battery negative material |
| CN109378458A (en) * | 2018-10-22 | 2019-02-22 | 东北大学 | It is a kind of to utilize the clay standby anode material of lithium-ion battery ZnS/C-SnO of tin2Method |
| CN110534727A (en) * | 2019-08-06 | 2019-12-03 | 中南大学 | A kind of tin zinc double metallic composite material and preparation method thereof |
| CN111017988A (en) * | 2019-12-31 | 2020-04-17 | 深圳爱多科传感技术有限公司 | Formaldehyde gas-sensitive material based on recovery treatment of tin mud and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113680374A (en) * | 2021-09-28 | 2021-11-23 | 中化学朗正环保科技有限公司 | Composite photocatalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113036113B (en) | 2022-06-03 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611409B (en) | Preparation method of flaky nano FeS2/C negative electrode material | |
| CN106450195B (en) | A kind of positive material for lithium-sulfur battery and preparation method thereof and the lithium-sulfur cell containing the positive electrode | |
| CN110474044A (en) | A kind of high-performance water system Zinc ion battery positive electrode and the preparation method and application thereof | |
| CN102280614B (en) | Preparation method of sulfur positive electrode of lithium sulfur battery | |
| CN103972497B (en) | Lithium ion battery Co2snO4/ C nano composite negative pole material and preparation and application thereof | |
| CN103928672B (en) | A kind of positive electrode active material for lithium ion battery and preparation method thereof | |
| CN111900346B (en) | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery | |
| CN109437339A (en) | Nickelic quaternary positive electrode material precursor and nickelic quaternary positive electrode, preparation method and purposes | |
| CN110429268A (en) | A kind of modified boron doping lithium-rich manganese-based anode material and the preparation method and application thereof | |
| CN107069001B (en) | Honeycomb zinc sulfide/carbon composite negative electrode material and preparation method thereof | |
| CN101916854A (en) | Preparation method of zinc sulfide/carbon composite material for negative electrode of lithium ion battery | |
| CN110994045B (en) | Zinc ion battery and manufacturing method thereof | |
| CN107093739B (en) | Potassium manganese oxide for potassium ion battery anode material and preparation method thereof | |
| CN111864200B (en) | High-capacity sodium ion battery positive electrode material | |
| CN103236518A (en) | Lithium ion battery negative nanometer material SnO2/MCMB (Mesophase Carbon Micro Beads) shell, and preparation method and application thereof | |
| CN109378458B (en) | Preparation of sodium ion battery negative electrode material ZnS/C-SnO by using tin mud2Method (2) | |
| CN109560258A (en) | A kind of anion appraises at the current rate layered oxide material, preparation method and purposes | |
| CN111600006B (en) | Preparation method of rod-like tin-antimony alloy as negative electrode material of lithium ion battery | |
| CN111960459A (en) | Preparation method of carbon-coated hollow capsule-shaped stannous sulfide/copper-tin bimetallic sulfide composite material, lithium battery cathode and battery | |
| CN110034342B (en) | Water system zinc-tellurium secondary battery | |
| CN105047870A (en) | Nitrogen-doped carbon-coated silicon composite material and preparation method thereof | |
| CN113036113B (en) | Doped BaSO4Sodium ion battery cathode material and preparation method thereof | |
| CN112242570B (en) | Application of mixture of carbon material and ionic bromide and aqueous zinc-bromine double-ion battery | |
| CN115611773B (en) | Lithium supplementing compound, preparation method thereof and lithium ion battery | |
| CN104882604A (en) | ZnS-Al2O3/N-C composite electrode material and preparation method |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220603 |