CN114368783B - Preparation method of magnesium ion battery anode material - Google Patents
Preparation method of magnesium ion battery anode material Download PDFInfo
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- CN114368783B CN114368783B CN202210137266.5A CN202210137266A CN114368783B CN 114368783 B CN114368783 B CN 114368783B CN 202210137266 A CN202210137266 A CN 202210137266A CN 114368783 B CN114368783 B CN 114368783B
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- polyacid
- magnesium ion
- sodium
- ion battery
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- 229910001425 magnesium ion Inorganic materials 0.000 title claims abstract description 48
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000010405 anode material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 136
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 136
- 239000007788 liquid Substances 0.000 claims abstract description 40
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 34
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims abstract description 26
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000007787 solid Substances 0.000 claims abstract description 17
- 238000000605 extraction Methods 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 12
- 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 abstract description 10
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 9
- CFVBFMMHFBHNPZ-UHFFFAOYSA-N [Na].[V] Chemical compound [Na].[V] CFVBFMMHFBHNPZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 8
- 230000001376 precipitating effect Effects 0.000 claims abstract description 5
- 150000003839 salts Chemical class 0.000 claims abstract description 3
- XONPDZSGENTBNJ-UHFFFAOYSA-N molecular hydrogen;sodium Chemical compound [Na].[H][H] XONPDZSGENTBNJ-UHFFFAOYSA-N 0.000 claims description 29
- 238000003756 stirring Methods 0.000 claims description 29
- 238000001556 precipitation Methods 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007774 positive electrode material Substances 0.000 claims description 18
- 229920002401 polyacrylamide Polymers 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 230000014759 maintenance of location Effects 0.000 claims description 11
- 159000000000 sodium salts Chemical class 0.000 claims description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 125000000129 anionic group Chemical group 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- -1 polyoxyethylene (oxypropylene) ether Polymers 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 239000012265 solid product Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000002994 raw material Substances 0.000 abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 5
- 230000008569 process Effects 0.000 abstract description 4
- 238000009388 chemical precipitation Methods 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 2
- 239000001257 hydrogen Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 54
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 10
- 239000011777 magnesium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000010406 cathode material Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 208000023445 Congenital pulmonary airway malformation Diseases 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910004283 SiO 4 Inorganic materials 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009830 intercalation Methods 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000002427 irreversible effect Effects 0.000 description 3
- 238000006479 redox reaction Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000009831 deintercalation Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910014079 Na—Mn—O Inorganic materials 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003872 anastomosis Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013211 curve analysis Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- NEMFQSKAPLGFIP-UHFFFAOYSA-N magnesiosodium Chemical compound [Na].[Mg] NEMFQSKAPLGFIP-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G31/00—Compounds of vanadium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a magnesium ion battery anode material, which comprises the following steps: a. adjusting the pH value of an extracting solution obtained by industrial vanadium extraction to be acidic, then carrying out desilication treatment, filtering, separating and collecting solid and liquid, wherein filtrate is vanadium qualified liquid; b. and adding sulfuric acid solution into the vanadium qualified liquid until the pH value is acidic, precipitating vanadium polyacid salt/vanadium polyacid, and filtering to obtain a solid which is the magnesium ion battery anode material. According to the invention, the complex sodium vanadate solution obtained by industrial vanadium extraction with high vanadium content is directly used as a raw material to replace a commercial vanadium-containing reagent, and the traditional hydrothermal method is replaced by a simple chemical precipitation method, so that the rapid and large-scale batch preparation of the vanadium sodium hydrogen polyacid/vanadium sodium polyacid/vanadium polyacid anode material can be realized, the production cost is greatly reduced, the whole process flow is simple to operate, and the method is compatible with the existing vanadium extraction process, thereby being very beneficial to industrial application.
Description
Technical Field
The invention relates to the technical field of magnesium ion batteries, in particular to a preparation method of a magnesium ion battery anode material.
Background
Rechargeable battery technology has greatly improved in terms of low cost, high energy density, etc., and is of great interest due to the rapid development of carbon-free transport and renewable energy sources. This trend has driven research into high energy lithium ion batteries. However, due to the safety problem of lithium dendrites, the method for preventing lithium dendrite formation is complicated, and the supply risk of lithium resources is based on Mg 2+ 、Ca 2+ 、Zn 2+ Or Al 3+ Alternative battery technologies for plasma multivalent ion transfer are of increasing interest.
Magnesium has an ultra-high theoretical volumetric energy density (3833 mAh.cm) -3 ) In addition, the magnesium resource is rich, and the magnesium ion batteryThese advantages make rechargeable magnesium ion batteries considered as one of the chemical energy storage devices that can continuously replace lithium electricity on a large scale, due to no magnesium dendrite deposition during charge and discharge. However, the development of magnesium ion battery technology is severely limited due to the strong coulombic effect of magnesium ions in the cathode material, poor compatibility of the magnesium ion cathode material and the electrolyte. Therefore, there is an urgent need to develop a high-performance rechargeable magnesium ion battery cathode material.
Currently, magnesium ion cathode materials are mainly concentrated into three major categories, namely transition metal sulfides, transition metal oxides and polyanionic compounds. As patent CN 112259733A discloses a method for preparing a magnesium ion battery positive electrode material with a nano-tubular molybdenum disulfide and octylamine composite structure by a one-step solvothermal method, the composite positive electrode material improves the conductivity and thermal stability of an electrode, but has still poor cycle performance (the capacity retention rate is only 33.33% after 100 cycles of cycle), and the discharge capacity is still low (the maximum initial discharge capacity is only 150 mah.g) -1 Left and right). Patent CN 111916700A discloses a method for preparing nano-sheet and nano-wire blended Na-Mn-O magnesium ion positive electrode material by hydrothermal method, the positive electrode material is 50 mA g -1 At the time, the maximum initial discharge capacity was 175 mAh.g -1 Although there has been a great improvement over some magnesium ion cathode materials, electrochemical energy storage requirements have not been met far enough. The preparation method of the material mainly adopts a hydrothermal method and a solvothermal method, and is long in time and high in energy consumption and has severe requirements on equipment. In addition, these materials all have problems of slow diffusion kinetics and low specific capacity, which slows down the development of magnesium ion cathode materials to some extent.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of a magnesium ion battery positive electrode material, so as to solve the problems of harsh preparation process of the magnesium ion battery positive electrode material and high requirements on raw material purity and production equipment in the prior art.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the magnesium ion battery anode material comprises the following steps:
a. adjusting the pH value of an extracting solution obtained by industrial vanadium extraction to be acidic, then carrying out desilication treatment, filtering, separating and collecting solid and liquid, wherein filtrate is vanadium qualified liquid;
b. and adding sulfuric acid solution into the vanadium qualified liquid until the pH value is acidic, precipitating vanadium polyacid salt/vanadium polyacid, and filtering to obtain a solid which is the magnesium ion battery anode material.
Preferably, the extracting solution obtained by the industrial vanadium extraction in the step a comprises, but is not limited to, vanadium-containing leaching solution obtained by sodium roasting-water leaching vanadium slag; and sodium vanadate solution obtained after adding sodium salt into other vanadium-containing liquid. If the solution obtained by preparing the sodium vanadate chemical reagent or the solution obtained by adding sodium salt after dissolving other vanadium-containing chemical reagents, the solution is directly regarded as vanadium qualified liquid.
Preferably, the concentration of vanadium element in the extracting solution obtained by industrial vanadium extraction is 10-50 g/L, and the concentration of silicon element is 0.2-5 g/L.
Preferably, in the step a, the pH of the extracting solution is adjusted to 2.4-5.0 by sulfuric acid.
Preferably, in the step a, the desilication treatment comprises the following steps: adding a desilication agent into the acidic extracting solution, stirring and reacting for 5-60 min at 20-70 ℃, and standing for 4-24 h.
Preferably, the desilication agent comprises one or more of zwitterionic polyacrylamide, nonionic polyacrylamide, cationic polyacrylamide, anionic polyacrylamide and nonionic polymeric flocculant polyoxyethylene (oxypropylene) ether.
Preferably, in the step a, the mass ratio of the desilicating agent to the silicon element in the extracting solution is 1.6-10:1.
Preferably, in step b, the precipitation of the vanadate/vanadate is carried out by adjusting the pH to obtain different precipitation products, in particular:
(1) When the pH value of the solution is 1.4-1.6, the precipitation product in the vanadium qualified liquid is vanadium polyacid H 4 V 12 O 32 And the content of vanadium polyacid in the precipitated product is more than 70%;
(2) When (when)When the pH value of the solution is 1.7-2.1, the precipitation product in the vanadium qualified liquid is sodium hydrogen vanadate NaHV 6 O 16 And the content of sodium hydrogen vanadate in the precipitated product is more than 80%;
(3) When the pH value of the solution is 2.2-3.0, the precipitation product in the vanadium qualified liquid is sodium vanadium polyacid NaV 3 O 8 And the content of sodium vanadate in the precipitated product is more than 80%.
Preferably, in the step b, the specific steps of precipitating vanadium from the sodium salt are as follows: and (3) dropwise adding a sulfuric acid solution with the pH value less than 3.0 into the vanadium qualified liquid to enable the pH value of the vanadium qualified liquid to reach a target value, stirring the vanadium qualified liquid at 80-100 ℃ for reaction for 50-250 min, cooling to room temperature, and filtering to obtain a required solid product.
According to the invention, the complex sodium vanadate solution with high vanadium content for industrial vanadium extraction is used as a raw material, and the desilication agent is used for effectively removing silicon element in the vanadium solution, so that vanadium loss is reduced. Under acidic condition, si in vanadium liquid is H 4 SiO 4 Exist and combine H through self O atom lone pair electron + Formation of H 5 SiO 4 + ，H 5 SiO 4 + And then combine with H 4 SiO 4 Forming positively charged colloidal particles. The silicon removing agent has a longer molecular chain structure, and the charges on the molecular chain can effectively neutralize the ion charges on the surfaces of the particles or near the surfaces of the particles to destroy the colloid structure, so that coarse solid particles are formed to precipitate, and the purpose of removing silicon is achieved. The types of precipitation products slightly change along with different pH values of the solution during precipitation, when the pH value is 1.4-1.6, the precipitation products are vanadium polyacids, when the pH value is 1.7-2.1, the precipitation products are vanadium polyacid sodium hydrogen, and when the pH value is 2.2-3.0, the precipitation products are vanadium polyacid sodium. Therefore, the formation of vanadium heteropoly acid can be inhibited by regulating and controlling the pH value change range and change speed of the vanadium-containing solution, the high-efficiency separation of vanadium and impurity elements can be realized, and the main reactions are as follows:
VO 3 - + 2H + = H 2 O + VO 2 + (1)
3VO 2 + + Na + + 2H 2 O = NaV 3 O 8 ↓ + 4H + (2)
6VO 2 + + Na + + 8H 2 O = NaHV 6 O 16 ·4H 2 O ↓ + 7H + (3)
12VO 2 + + 8H 2 O = H 4 V 12 O 32 ↓ + 12H + (4)
compared with the prior art, the invention has the following beneficial effects:
1. according to the invention, the industrial vanadium extraction complex solution with high vanadium content is directly adopted as a raw material to replace commercial vanadium-containing chemical raw materials, and the traditional hydrothermal method is replaced by a simple chemical precipitation method, so that the rapid and large-scale batch preparation of the vanadium sodium hydrogen polyacid/vanadium sodium polyacid/vanadium polyacid anode material can be realized, the production cost is greatly reduced, the production efficiency is remarkably improved, the whole process flow is simple to operate, and the method is compatible with the existing vanadium extraction process, thereby being very beneficial to the industrial application.
2. The vanadium polyacid sodium hydrogen/vanadium polyacid sodium/vanadium polyacid prepared by the method of the invention is taken as the magnesium ion battery anode material, and shows high specific capacity (current density is mA.g) -1 The time specific capacity is 404.35 mAh.g -1 ) Ultra-long cycle stability (current density of 1A g) -1 The capacity retention rate is 97.45% after 310 times of time circulation), and the higher rate capability (20 times to 2A g in current density increase) -1 The specific capacity was 135.67 mAh g -1 The retention rate of specific capacity is 33.55 percent, solves the problems of slow diffusion dynamics and low specific capacity in the existing magnesium storage technology, and is a magnesium ion battery anode material with excellent performance.
Drawings
FIG. 1 is an X-ray diffraction pattern of sodium hydrogen vanadate prepared in example 2.
FIG. 2 shows the voltage sweep rate of 1 mV s -1 Cyclic voltammograms at different cycles of sample preparation at different pH conditions: (a) ph=1.4 to 1.6, (b) ph=1.7 to 2.1, (c) ph=2.2 to 3.
FIG. 3 shows a current density of 50-2000 mA.g -1 Under different pH conditionsConstant current charge-discharge curve for the sample: (a) ph=1.4 to 1.6, (b) ph=1.7 to 2.1, (c) ph=2.2 to 3.
FIG. 4 shows a current density of 50-1000 mA.g -1 Magnification bar graph of samples prepared at different pH conditions: (a) ph=1.4 to 1.6, (b) ph=1.7 to 2.1, (c) ph=2.2 to 3.
FIG. 5 shows a constant current density of 1000 mA g -1 Cyclic stability test patterns of samples prepared at different pH conditions: (a) ph=1.4 to 1.6, (b) ph=1.7 to 2.1, (c) ph=2.2 to 3.
Fig. 6 is a process flow diagram of the present invention.
Detailed Description
The invention will be further described with reference to the drawings and examples.
It should be understood by those skilled in the art that the detailed description is intended to illustrate and explain the invention, and not to limit the invention. Accordingly, substitutions and alterations are possible to the examples described above without departing from the spirit and scope of the claims.
1. Preparation method of magnesium ion battery anode material
In the prior art, the sodium vanadium polyacid/the sodium vanadium polyacid has a unique porous layered structure and interlayer structural water, the porous layered structure can provide a transmission channel for magnesium ions to quickly insert/release, the interlayer structural water can shield strong electrostatic interaction between the magnesium ions of a guest and a lattice framework, the diffusion dynamics condition of the magnesium ions in the interlayer structural water is excellent, and the problem of slow magnesium ion diffusion dynamics of the anode material of the traditional magnesium ion battery can be solved. Meanwhile, the supporting function of the structural water can keep the porous layered structure stable, the problem of poor cycle performance of the traditional magnesium ion battery anode material can be solved, and positive vanadium valence states are changeable, and a single vanadium atom can store a plurality of electrons, so that the theoretical specific capacitance of the material is high. However, there is no report on the related art for synthesizing sodium hydrogen vanadate/sodium vanadate/vanadate.
Example 1:
(1) Desilication of sodium vanadate solution: 50 And (3) regulating the pH value of the sodium vanadate solution to be 3.2 by using sulfuric acid, adding 0.2g anionic polyacrylamide CPAM, stirring at the stirring speed of 200r/min at normal temperature for reacting for 30min, standing for 14h, filtering, washing filter residues with deionized water for 2-3 times, and carrying out secondary filtering. The desilication rate is measured to be 84.37%, the vanadium loss rate is measured to be 1.24%, and the filtrate is called vanadium qualified liquid;
(2) Sodium salt precipitation of vanadium qualified liquid: and (3) dropwise adding the qualified vanadium solution into a sulfuric acid solution with the concentration of 0.5mol/L while stirring at room temperature until the pH value of the mixed solution is=1.6, stirring the mixed solution at the temperature of T=90 ℃ at the stirring speed of 200r/min for reaction for 60min, naturally cooling the solution to room temperature, filtering and separating solid and liquid, and collecting the solid for later use. The vanadium precipitation rate is 96.71 percent through detection.
Example 2:
(1) Desilication of sodium vanadate solution: 50mL of sodium vanadate solution (the content of vanadium element is 41.79g/L and the content of silicon element is 1.2585 g/L), regulating the pH value of the sodium vanadate solution to be 3.2 by sulfuric acid, adding 0.2g of anionic polyacrylamide CPAM, stirring at the stirring speed of 200r/min at normal temperature for reaction for 30min, standing for 14h, filtering, washing filter residues with deionized water for 2-3 times, and performing secondary filtering. The desilication rate is measured to be 84.21%, the vanadium loss rate is measured to be 1.15%, and the filtrate is called vanadium qualified liquid;
(2) Sodium salt precipitation of vanadium qualified liquid: and (3) dropwise adding the qualified vanadium solution into a sulfuric acid solution with the concentration of 0.5mol/L while stirring at room temperature until the pH value of the mixed solution is=1.8, stirring the mixed solution at the temperature of T=90 ℃ at the stirring speed of 200r/min for reaction for 60min, naturally cooling the solution to room temperature, filtering and separating solid and liquid, and collecting the solid for later use. The vanadium precipitation rate is 96.72 percent through detection.
Example 3:
(1) Desilication of sodium vanadate solution: 50mL of sodium vanadate solution, regulating the pH value to be 2.4 by sulfuric acid, adding 0.1g of anionic polyacrylamide CPAM, stirring at the normal temperature at the stirring speed of 200r/min for reaction for 50min, standing for 14h, filtering, washing filter residues with deionized water for 2-3 times, and carrying out secondary filtering. The desilication rate is 86.04 percent, the vanadium loss rate is 0.19 percent, and the filtrate is called vanadium qualified liquid;
(2) Sodium salt precipitation of vanadium qualified liquid: and (3) dropwise adding the qualified vanadium solution into a sulfuric acid solution with the concentration of 1mol/L while stirring at room temperature until the pH value of the mixed solution is=1.8, stirring the mixed solution at the temperature of T=90 ℃ at the stirring speed of 200r/min for reaction for 90min, naturally cooling the solution to room temperature, filtering and separating solid and liquid, and collecting the solid for later use. The vanadium precipitation rate is 95.58 percent through detection.
Example 4:
(1) Desilication of sodium vanadate solution: 50mL of sodium vanadate solution, regulating the pH value of the solution to be 3.0 by sulfuric acid, adding 0.1g of anionic polyacrylamide CPAM, stirring at the stirring speed of 200r/min at normal temperature for reacting for 60min, standing for 14h, filtering, washing filter residues with deionized water for 2-3 times, and carrying out secondary filtering. The desilication rate is 88.08 percent, the vanadium loss rate is 0.082 percent, and the filtrate is called vanadium qualified liquid;
(2) Sodium salt precipitation of vanadium qualified liquid: and (3) dropwise adding the qualified vanadium solution into a 1mol/L sulfuric acid solution while stirring at room temperature until the pH value of the mixed solution is=2.0, stirring the mixed solution at the temperature of T=90 ℃ at the stirring speed of 200r/min for reaction for 90min, naturally cooling the solution to room temperature, filtering and separating solid and liquid, and collecting the solid for later use. The vanadium precipitation rate is 94.9% through detection.
Example 5:
(1) Desilication of sodium vanadate solution: 50mL of sodium vanadate solution, regulating the pH value of the solution to be 3.0 by sulfuric acid, adding 0.1g of anionic polyacrylamide CPAM, stirring at the stirring speed of 200r/min at normal temperature for reacting for 60min, standing for 14h, filtering, washing filter residues with deionized water for 2-3 times, and carrying out secondary filtering. The desilication rate is 87.23 percent, the vanadium loss rate is 0.24 percent, and the filtrate is called vanadium qualified liquid;
(2) Sodium salt precipitation of vanadium qualified liquid: and (3) dropwise adding the qualified vanadium solution into a 1mol/L sulfuric acid solution while stirring at room temperature until the pH value of the mixed solution is=2.4, stirring the mixed solution at the temperature of T=90 ℃ at the stirring speed of 200r/min for reaction for 90min, naturally cooling the solution to room temperature, filtering and separating solid and liquid, and collecting the solid for later use. The vanadium precipitation rate is 94.5% through detection.
2. Phase characterization of the preparation of the product
FIG. 1 is an XRD analysis of sodium hydrogen vanadate prepared in example 2, with diffraction peaks vs. NaHV 6 O 16 ·4H 2 The anastomosis of O indicates thatThe prepared product is NaHV 6 O 16 ·4H 2 O. The sample products prepared in examples 3 and 4 were examined in the same manner and the results were substantially identical to those of example 2.
3. Characterization of the electrochemical Properties of the preparation of the product
The vanadium polyacid, the sodium hydrogen vanadate and the sodium vanadate prepared in examples 1, 3 and 5 are respectively added into N-methylpyrrolidone (NMP) solution with the conductive agent acetylene black and the adhesive polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, ground and mixed to slurry, and uniformly coated on a carbon cloth electrode with a rectangular shape of 1X 1.5 cm, wherein the coating area is 1 cm 2 And drying 24-h in a vacuum drying oven at 80 ℃ to obtain the positive pole piece of the magnesium ion battery.
The electrochemical performance test of the invention adopts a three-electrode electrochemical cell to represent the intrinsic electrochemical performance of the material, vanadium polyacid, sodium hydrogen vanadate and sodium vanadate are respectively used as active materials to be loaded on carbon cloth as a working electrode, a graphite sheet as a counter electrode and a saturated calomel electrode as a reference electrode, and 0.5mol/L MgCl is used as a working electrode 2 Performing electrochemical performance test on the electrolyte; the electrochemical workstation (CHI 660E) is used for respectively carrying out Cyclic Voltammetry (CV) and constant current charge-discharge (GCD) tests on the vanadium polyacid sodium hydrogen anode material.
(1) Cyclic voltammetry test
FIG. 2 shows that the voltage scan rate of a magnesium ion battery with vanadium polyacid, sodium hydrogen vanadate and sodium vanadate as positive electrode materials is 1 mV s -1 And (3) circulating a cyclic voltammogram (CV curve) with different circles, wherein a voltage window is-0.8V. As can be seen from fig. 2, the CV curve of the vanadium polyacid has only one irreversible oxidation reaction (about 0.4V), and the CV curves of the sodium hydrogen vanadium polyacid and the sodium vanadium polyacid are similar, and there are a pair of oxidation-reduction reactions (-0.085V, -0.303V) and one irreversible oxidation reaction (0.275V), but as the number of reaction turns increases, the oxidation peak at-0.085V gradually decreases and the oxidation peak at 0.275V gradually increases, and at the same time, the shape of the whole CV curve is changed from the battery type per se to the pseudocapacitance type, and the change of the oxidation-reduction peak is necessarily related to the change. Wherein, inThe oxidation-reduction reaction equation of the vanadium polyacid sodium hydrogen positive electrode material at or near the surface is as follows:
NaHV 6 O 16 ·4H 2 O + xMg 2+ + xe - = Mg x NaHV 6 O 16 ·4H 2 O （3）
NaHV 6 O 16 ·4H 2 o has a lamellar structure similar to graphene, and structural water exists in the crystal, which is very beneficial to the intercalation and deintercalation of ions or electrons, and x in the formula (3) refers to intercalation of NaHV 6 O 16 ·4H 2 Mg between O layers 2+ Number of moles.
(2) Constant current charge-discharge and rate capability test
FIG. 3 shows an electrolyte of 0.5mol/L MgCl 2 When the vanadium polyacid, the sodium hydrogen vanadate and the sodium vanadate are used as constant current charge-discharge curves (GCD) of the positive electrode material under different current densities. As can be seen from fig. 3, the GCD curves of the three materials neither have a very pronounced voltage plateau nor are they linear, indicating that faraday pseudocapacitance occurs during charge and discharge, consistent with the results of CV curve analysis. Wherein the vanadium polyacid has low charge-discharge specific capacity and poor reversibility, and the current density is 500 mA g -1 The maximum specific charge and discharge capacities are 140.23 mAh.g respectively -1 And 218.31 mAh.g -1 The irreversible capacity is consistent with CV analysis result, and the specific charge and discharge capacities of the sodium hydrogen vanadate and the sodium vanadate are equivalent, when the current density is mA.g -1 When the sodium hydrogen vanadate has a specific capacity of 404.35 mAh.g -1 The specific capacity gradually decreases with increasing current density, since the greater the current density, the more Mg 2+ And not participate in the redox reaction occurring on the surface of the material, resulting in a decrease in specific capacity.
Fig. 4 shows the results of testing three materials at different rates. Wherein, the multiplying power performance of the sodium hydrogen vanadate and the sodium vanadate is similar and superior to that of the vanadium polyacid. When the current density is from 500 mAh.g -1 Increase to 1000 mAh.g -1 When the capacity retention rate of the vanadium polyacid was 18.14%. When electricity is generatedThe flow density was 50 mA g -1 When the specific capacity of the sodium hydrogen vanadate is 404.35 mAh.g -1 . When the current density increases to 1A g -1 The specific capacity retention rate was 37.37%. This shows that the positive electrode materials of the vanadium polyacid sodium hydrogen and vanadium polyacid sodium magnesium ion batteries have better multiplying power performance.
(3) Cycle stability test
The three magnesium ion batteries prepared above were mixed at 1A g -1 The stability of the positive electrode material is tested under the conditions that the current density and voltage window are-0.8V and constant current charge and discharge cycle is 310 times, and the specific capacity of the three positive electrode materials under different cycle times is shown in figure 5. After 250-380 cycles, the capacity retention rates of the vanadium polyacid, the sodium hydrogen vanadate and the sodium vanadium polyacid are 91%, 97% and 76%, respectively, which shows that the magnesium ion battery positive electrode material prepared by the invention has excellent cycle stability and ultra-long cycle life, and the advantages exhibited by the sodium hydrogen vanadium polyacid are possibly related to larger interlayer spacing of the material, and are more beneficial to the intercalation and deintercalation of magnesium ions.
In conclusion, the vanadium polyacid sodium hydrogen/vanadium polyacid sodium/vanadium polyacid prepared by the method of the invention is taken as the positive electrode material of the magnesium ion battery, and shows high specific capacity (current density is 50 mA g) -1 The time specific capacity is 404.35 mAh.g -1 ) Ultra-long cycle stability (current density of 1A g) -1 The capacity retention rate is 97.45% after 310 times of time circulation), and the higher rate capability (20 times to 2A g in current density increase) -1 The specific capacity was 135.67 mAh g -1 The retention rate of specific capacity is 33.55 percent, solves the problems of slow diffusion dynamics and low specific capacity in the existing magnesium storage technology, and is a magnesium ion battery anode material with excellent performance. According to the invention, the industrial vanadium extraction complex vanadium-containing solution with high vanadium content is used as a raw material, the traditional hydrothermal method is replaced by a simple chemical precipitation method, so that the rapid and large-scale batch preparation of the vanadium polyacid sodium hydrogen/vanadium polyacid sodium/vanadium polyacid anode material can be realized, the production cost is greatly reduced, the production efficiency is remarkably improved, the whole process flow is simple to operate, and the method is compatible with the existing vanadium extraction process, thereby being very beneficial to the industrial application of the vanadium polyacid sodium hydrogen/vanadium polyacid sodium/vanadium polyacid anode material.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the technical solution, and those skilled in the art should understand that modifications and equivalents may be made to the technical solution of the present invention without departing from the spirit and scope of the present invention, and all such modifications and equivalents are included in the scope of the claims.
Claims (3)
1. The preparation method of the magnesium ion battery anode material is characterized by comprising the following steps of:
a. adjusting the pH value of an extracting solution obtained by industrial vanadium extraction to be acidic, then carrying out desilication treatment, filtering, separating and collecting solid and liquid, wherein filtrate is vanadium qualified liquid;
b. adding sulfuric acid solution into the vanadium qualified liquid until the pH value is acidic, precipitating vanadium polyacid salt/vanadium polyacid, and filtering to obtain a solid which is the magnesium ion battery anode material;
in the step b, when the vanadium polyacrylate/vanadium polyacid is precipitated, different precipitation products are obtained by adjusting the pH value, specifically:
(1) When the pH value of the solution is 1.4-1.6, the precipitation product in the vanadium qualified liquid is vanadium polyacid H 4 V 12 O 32 And the content of vanadium polyacid in the precipitated product is more than 70%;
(2) When the pH value of the solution is 1.7-2.1, the precipitation product in the vanadium qualified liquid is sodium hydrogen vanadate NaHV 6 O 16 And the content of sodium hydrogen vanadate in the precipitated product is more than 80%;
(3) When the pH value of the solution is 2.2-3.0, the precipitation product in the vanadium qualified liquid is sodium vanadium polyacid NaV 3 O 8 And the content of sodium vanadate in the precipitated product is more than 80%;
the vanadium polyacid, the sodium hydrogen vanadate and the sodium vanadate are adopted as positive electrode active materials to prepare the magnesium ion battery, when the current density is 500 mA g -1 When the magnesium ion battery takes vanadium polyacid as an active material, the maximum charge and discharge specific capacities of the magnesium ion battery are 140.23 mAh.g respectively -1 And 218.31 mAh.g -1 And when the current density is from 500 mAh.g -1 Increase to 1000 mAh.g -1 When the capacity retention rate was 18.14%;
when the current density is 50 mA g -1 When the magnesium ion battery takes sodium hydrogen vanadate as an active material, the maximum specific capacity of the magnesium ion battery is 404.35 mAh.g -1 And when the current density is increased to 1A g -1 The retention of the specific capacity was 37.37%;
at 1A g -1 Under the conditions that the current density and voltage window are-0.8V and constant current charge and discharge cycle is 310 times, the capacity retention rates of the magnesium ion battery prepared by taking vanadium polyacid, vanadium polyacid sodium hydrogen and vanadium polyacid sodium as positive electrode active materials are 91%, 97% and 76% respectively;
in the step a, the pH of the extracting solution is adjusted to 2.4-5.0 by sulfuric acid;
in step a, the desilication treatment comprises the following steps: adding a desilication agent into the acidic extracting solution, stirring and reacting for 5-60 min at 20-70 ℃, and standing for 4-24 h; the desilication agent comprises one or more of zwitterionic polyacrylamide, nonionic polyacrylamide, cationic polyacrylamide, anionic polyacrylamide and nonionic polymeric flocculant polyoxyethylene (oxypropylene) ether; the mass ratio of the desilication agent to the silicon element in the extracting solution is 1.6-10:1;
in the step b, the specific steps of precipitating vanadium from the sodium salt are as follows: and (3) dropwise adding a sulfuric acid solution with the pH value less than 3.0 into the vanadium qualified liquid to enable the pH value of the vanadium qualified liquid to reach a target value, stirring the vanadium qualified liquid at 80-100 ℃ for reaction for 50-250 min, cooling to room temperature, and filtering to obtain a required solid product.
2. The method for preparing the magnesium ion battery positive electrode material according to claim 1, wherein the extracting solution obtained by industrial vanadium extraction in the step a comprises, but is not limited to, vanadium-containing leaching solution obtained by sodium roasting-water leaching of vanadium slag; and sodium vanadate solution obtained after adding sodium salt into other vanadium-containing liquid.
3. The method for preparing the magnesium ion battery positive electrode material according to claim 2, wherein the concentration of vanadium element in the extracting solution obtained by industrial vanadium extraction is 10-50 g/L, and the concentration of silicon element is 0.2-5 g/L.
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