CN117727938A - Sodium ion battery positive electrode material capable of being used for quick charge and preparation method thereof - Google Patents
Sodium ion battery positive electrode material capable of being used for quick charge and preparation method thereof Download PDFInfo
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- CN117727938A CN117727938A CN202410172955.9A CN202410172955A CN117727938A CN 117727938 A CN117727938 A CN 117727938A CN 202410172955 A CN202410172955 A CN 202410172955A CN 117727938 A CN117727938 A CN 117727938A
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- Prior art keywords
- positive electrode
- electrode material
- sodium
- ion battery
- sodium ion
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 79
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 50
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000011734 sodium Substances 0.000 claims abstract description 59
- 239000011572 manganese Substances 0.000 claims abstract description 33
- 239000002131 composite material Substances 0.000 claims abstract description 28
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical group [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000010410 layer Substances 0.000 claims abstract description 8
- 239000012792 core layer Substances 0.000 claims abstract description 6
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 32
- 239000012266 salt solution Substances 0.000 claims description 31
- 239000011777 magnesium Substances 0.000 claims description 30
- 239000002245 particle Substances 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 17
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002243 precursor Substances 0.000 claims description 16
- 238000001354 calcination Methods 0.000 claims description 14
- 238000005086 pumping Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 10
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000498 ball milling Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 230000001965 increasing effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052736 halogen Inorganic materials 0.000 claims description 6
- -1 halogen salt Chemical class 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- PFUVRDFDKPNGAV-UHFFFAOYSA-N sodium peroxide Chemical compound [Na+].[Na+].[O-][O-] PFUVRDFDKPNGAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 159000000003 magnesium salts Chemical class 0.000 claims description 4
- 150000002696 manganese Chemical class 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 150000003388 sodium compounds Chemical class 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000000975 co-precipitation Methods 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 239000006104 solid solution Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 2
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 claims description 2
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 2
- NESLWCLHZZISNB-UHFFFAOYSA-M sodium phenolate Chemical compound [Na+].[O-]C1=CC=CC=C1 NESLWCLHZZISNB-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 8
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 230000037427 ion transport Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 239000002244 precipitate Substances 0.000 description 9
- 239000011257 shell material Substances 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 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 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 239000012716 precipitator Substances 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 230000001502 supplementing effect Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention relates to a sodium ion battery positive electrode material for quick charge and a preparation method thereof, which is a composite positive electrode material with a core-shell structure, wherein a core layer is nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 Wherein 0 < x < 1,0 < y < 1,0 < z < 1, x+y+z=1; the shell layer material is BNT, and the doping proportion of BNT in the composite positive electrode material is 1-5 wt%. The proposal of the invention mainly utilizes the ferroelectric effect and the piezoelectric effect of BNT to form a local micro-electric field so as to promote sodium ion transport and improve Na + Ion diffusion kinetics is greatly improved, so that the potential anode material of the fast-chargeable sodium ion battery is finally prepared, the problems of slow kinetics and the like caused by larger radius of sodium ions are solved, and meanwhile, the structural stability of the anode material is further enhanced, so that the anode material has good multiplying power performance and circulation stability.
Description
Technical Field
The invention relates to the technical field of electrochemical materials, in particular to a sodium ion battery positive electrode material capable of being used for quick charge and a preparation method thereof.
Background
The sodium ion battery has a similar chemical reaction mechanism as the lithium ion battery, and the production process and the production equipment can be used universally, so that the sodium ion battery has a larger advantage in cost than the lithium ion battery. Therefore, the sodium ion battery can be used as a beneficial supplement of the lithium ion battery and is even expected to become a substitute of the lithium ion battery, and the positive electrode material is a key of industrialization, wherein the transition metal oxide positive electrode material with high specific capacity is widely paid attention to and studied by those skilled in the art. However, the rate performance is limited by problems such as slow kinetics due to the large radius of sodium ions. In addition, the transition metal oxide positive electrode material of the sodium ion battery can generate complex phase change in the charge and discharge process, and the material structure is unstable and the battery cycle performance is low.
Therefore, how to improve the diffusion kinetics of the positive electrode material of the sodium ion battery and the stability of the reinforcing material become key problems for improving the performance of the sodium ion battery.
Disclosure of Invention
First, the technical problem to be solved
In view of the above-mentioned shortcomings and drawbacks of the prior art, the present invention provides a method ofPositive electrode material for sodium ion battery for quick charge and its preparation method, which adopts leadless piezoelectric ceramics (Bi 0.5 Na 0.5 )TiO 3 And nickel-manganese-based layered oxide to obtain a composite positive electrode material, using (Bi 0.5 Na 0.5 )TiO 3 Forms a local micro-electric field with the ferroelectric effect and the piezoelectric effect to promote sodium ion transport and improve Na + Ion diffusion kinetics is greatly improved, so that the potential anode material of the fast-chargeable sodium ion battery is finally prepared, the problems of slow kinetics and the like caused by larger radius of sodium ions are solved, and the structural stability of the anode material is enhanced.
(II) technical scheme
In a first aspect, the present invention provides a method for preparing a positive electrode material for a fast-charging sodium ion battery, which is a composite positive electrode material with a core-shell structure, wherein a core layer is a nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x+y+z=1; the shell layer material is (Bi) 0.5 Na 0.5 )TiO 3 And (Bi) 0.5 Na 0.5 )TiO 3 The doping proportion in the composite positive electrode material is 1-5wt.%; the preparation method comprises the following steps:
s1, preparing a metal salt solution, wherein the metal salt solution contains nickel, manganese and magnesium metal ions,
pumping the metal salt solution, the complexing agent solution and the precipitant solution into a reactor at the same time to carry out coprecipitation reaction, washing a precipitated product after the reaction is finished, and drying to obtain a positive electrode material precursor;
s2, mixing and calcining the positive electrode material precursor and a sodium compound, cooling to room temperature, crushing and sieving to obtain a nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x+y+z=1;
s3, preparing nickel-manganese-based layered oxide anode material Na 0.67 Ni x Mn y Mg z O 2 Mixing with BNT in the presence of solvent by wet ball millingAfter uniform suction filtration, sintering and solid solution reaction are carried out on the filter cake to obtain the composite anode material Na 0.67 Ni x Mn y Mg z O 2 BNT coated on nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 And an exterior.
According to a preferred embodiment of the present invention, x=0.24-0.28, y=0.67, z=0.05-0.09.
According to the preferred embodiment of the present invention, in S1, the raw materials used for preparing the metal salt solution include nickel salt, manganese salt and magnesium salt, wherein the nickel salt is at least one of sulfate, nitrate and halogen salt of nickel; the manganese salt is at least one of sulfate, nitrate and halogen salt of manganese; the magnesium salt is at least one of sulfate, nitrate and halogen salt of magnesium.
According to a preferred embodiment of the invention, in S1, the total concentration of metal ions in the metal salt solution is 0.5-2M, preferably 0.5M, 0.6M, 0.7M, 0.8M, 0.9M, 1.0M, 1.1M, 1.2M, 1.3M, 1.4M, 1.5M or 1.8M; wherein, the molar ratio of the nickel, manganese and magnesium elements can be any preset ratio as long as the total concentration of metal ions in the metal salt solution is 0.5-2M. The total concentration of metal ions in the metal salt solution cannot be excessively high (> 2M), otherwise, the precursor of the nickel-manganese-based layered oxide positive electrode material with uniformly distributed metal elements is difficult to obtain; if the total concentration of metal ions in the metal salt solution is too low (< 0.5M), the product preparation efficiency is too low, and a large amount of precipitants and complexing agents are wasted.
Wherein BNT is 1-5%, e.g., 1%, 2%, 3%, 4% or 5% of the mass of the composite positive electrode material. If the content ratio of BNT is too high, the content of the nickel-manganese-based layered oxide cathode material is too low, the rate performance and the cycle stability of the battery cathode material are reduced, and if the content of BNT is too low, the effects of effectively promoting sodium ion transport and enhancing the structural stability of the composite cathode material cannot be achieved.
According to a preferred embodiment of the present invention, in S1, the complexing agent solution is ammonia water, and the precipitant solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
According to the preferred embodiment of the invention, in S1, the reactor is preheated and heated, the stirring of the reactor is started, the rotating speed is 200-350rpm, then ammonia water, precipitant solution and metal salt solution are pumped into the reaction kettle at a low speed, the particle size of product particles is observed, when the particle size D50 of the product particles is 4.0 mu m, the pumping speed of the metal salt solution is increased, the particle size D50 of the product particles is 10.0 mu m, the pumping of the metal salt solution is stopped, and the reaction is completed. Thus, the particle size of the positive electrode material precursor material and the final composite positive electrode material can be controlled. In the reaction process, the stirring speed is not too high, so that the positive electrode material precursor material with the required particle size is not easy to form, and the stirring speed is too low, so that the distribution of each metal element in the product is not uniform.
Specifically, for a small-sized reaction kettle of 0.5-1L, firstly preheating the reaction kettle to 40 ℃, starting stirring, stirring at a speed of 300rpm, then pumping ammonia water, a precipitant solution and a metal salt solution into the reaction kettle at a flow rate of 50mL/min respectively, observing the particle size of product particles, and independently increasing the pumping speed of the metal salt solution to 80mL/min until the particle size D50 of the product particles is 4.0 mu m, and stopping the reaction until the particle size D50 of the product particles is 10.0 mu m.
According to a preferred embodiment of the present invention, in S1, the water washing conditions are: washing with deionized water at 45-55deg.C for 4-5 times; the drying conditions are as follows: drying and dehydrating at 110-120deg.C for 8 hr, taking out, sealing and storing.
According to a preferred embodiment of the present invention, in S2, the sodium compound is at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate, and sodium phenolate.
According to a preferred embodiment of the present invention, in S2, the conditions of the calcination treatment are: heating to 600-1050 ℃ at a heating rate of 3-10 ℃/min, and calcining for 5-36h; preferably at 800-850 deg.c for 10-15 hr.
According to a preferred embodiment of the invention, in S2, the calcination is performed under an atmosphere of air, oxygen or argon.
According to a preferred embodiment of the invention, in S3, the ball milling time is 1-3 hours.
According to a preferred embodiment of the present invention, in S3, the solvent used for wet ball milling is at least one of water, ethanol, N-methylpyrrolidone and acetone.
According to a preferred embodiment of the present invention, in S3, the sintering conditions are: heating to 500-950 ℃ at a heating rate of 3-10 ℃/min, calcining for 5-36h, and using argon as a protective atmosphere in the sintering process; preferably at 500-600 deg.c for 15-20 hr.
The invention also provides a sodium ion battery positive electrode material which is prepared by adopting the preparation method of any embodiment and can be used for quick charge.
(III) beneficial effects
(1) The sodium ion battery anode material is a composite anode material, and specifically adopts (Bi 0.5 Na 0.5 )TiO 3 For the shell layer material, the nickel-manganese base layered oxide anode material Na 0.67 Ni x Mn y Mg z O 2 Coating, forming a local micro-electric field by ferroelectric effect and piezoelectric effect generated by the shell material to promote sodium ion transport, and improving Na + Ion diffusion kinetics solves the problems of slow kinetics and the like caused by larger radius of sodium ions, thereby greatly improving the rate performance, and being a potential anode material of a fast-chargeable sodium ion battery.
(2) Shell material (Bi) 0.5 Na 0.5 )TiO 3 Solid solution is generated in the sintering process, so that the structural stability of the positive electrode material can be greatly improved, and the problems of unstable material structure and rapid decay of battery cycle performance caused by complex phase change in the charging and discharging process are prevented. The existence of the coating layer can effectively reduce the dissolution of the electrolyte to the nickel-manganese-based layered oxide cathode material, thereby remarkably improving the stability of the cathode material structure.
(3) In the composite positive electrode material of the present invention, the shell layer material (Bi 0.5 Na 0.5 )TiO 3 Also has sodium, which has the function of sodium supplementing agent, increases the concentration of sodium ions contained in the positive electrode composite material, and has the function of sodium supplementing agent for Na + The ion diffusion movement forms chemical power and also helpsTo increase the energy density of the battery. If other piezoelectric ceramic materials are replaced (Bi 0.5 Na 0.5 )TiO 3 On one hand, the material cannot generate ferroelectric effect or serve as a sodium supplementing agent, and the shell material occupies a certain space, so that the concentration of sodium ions can be diluted, and the energy density of the battery is reduced.
(4) The nickel-manganese-based layered oxide positive electrode material precursor is prepared by adopting a coprecipitation method, and the nickel-manganese-based sodium ion battery positive electrode material coated by the ferroelectric material is prepared by mixing sodium and calcining, so that the preparation process does not contain expensive transition metal material cobalt, the production cost is greatly reduced, and the industrial popularization and application of related products are facilitated. In the preparation process, the anode precursor (D50 is 10.0 mu m) with the preset particle size and the composite anode material are further obtained by controlling the pumping speed of the complexing agent, the precipitator and the metal salt solution, observing the particle size of precursor particles suspended in a reaction system and adjusting the feeding speed in real time.
Drawings
FIG. 1 shows Na prepared in example 1 of the present invention 0.67 Ni x Mn y Mg z O 2 SEM image of composite positive electrode material of BNT sodium ion battery.
Detailed Description
The invention will be better explained by the following detailed description of the embodiments with reference to the drawings.
Example 1
The sodium ion battery positive electrode material for quick charge is prepared by the embodiment, is a composite positive electrode material with a core-shell structure, and a core layer is nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni 0.28 Mn 0.67 Mg 0.05 O 2 The shell layer material is (Bi) 0.5 Na 0.5 )TiO 3 And (Bi) 0.5 Na 0.5 )TiO 3 The doping ratio in the composite positive electrode material was 1wt.%. The preparation method comprises the following steps:
(1) Nickel sulfate, manganese sulfate and magnesium sulfate (molar ratio 28:67:5) are added into deionized water to prepare a ternary metal salt solution with the total metal ion concentration of 2 mol/L. Simultaneously preparing 2mol/L sodium carbonate solution and 2mol/L ammonia water which are respectively used as a precipitator and a complexing agent.
(2) The temperature of the reaction kettle is raised to 40 ℃, ammonia water, sodium bicarbonate solution and metal salt solution are slowly pumped into the reaction kettle at the flow rate of 50ml/min under the stirring rate of 300r/min until the D50 of the precipitated particles is 4.0 mu m, then the pumping speed of the metal salt solution is increased to 80ml/min until the D50 of the precipitated particles is 10.0 mu m, and the reaction is stopped.
(3) The precipitate was separated and washed by centrifugation with deionized water at 50 ℃ for 5 times.
(4) Dispersing the precipitate after centrifugal washing, putting the precipitate into a vacuum oven, and drying and dehydrating for 8 hours at 120 ℃ to obtain a positive electrode material precursor Ni 0.28 Mn 0.67 Mg 0.05 CO 3 Sealing and storing.
(5) Mixing the precursor of the positive electrode material and sodium peroxide according to the element molar ratio (Ni+Mn+Mg): na=1:0.67, heating to 830 ℃ in a muffle furnace at a heating rate of 5 ℃/min, calcining for 15 hours, cooling, crushing and sieving to obtain the layered oxide positive electrode material.
(6) 495g of layered oxide positive electrode material and 5g (Bi) 0.5 Na 0.5 )TiO 3 Transferring into a ball mill, adding a small amount of ethanol, performing wet ball milling for 1h, transferring into a sintering furnace, heating to 500 ℃ at a speed of 3 ℃/min under the protection atmosphere of argon, maintaining the constant temperature for 20h, and naturally cooling to obtain Na 0.67 Ni 0.28 Mn 0.67 Mg 0.05 O 2 @ (Bi 0.5 Na 0.5 )TiO 3 A composite positive electrode material in which (Bi 0.5 Na 0.5 )TiO 3 The content was 1wt.%.
As shown in FIG. 1, na prepared according to the present invention 0.67 Ni x Mn y Mg z O 2 SEM image of the composite positive electrode material of BNT sodium ion battery, with a median particle size D50 of about 10.0 μm.
Example 2
The embodiment prepares a sodium ion battery anode material for quick charge, which is a core-shellComposite positive electrode material with structure, and core layer of nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni 0.26 Mn 0.67 Mg 0.07 O 2 The shell layer material is (Bi) 0.5 Na 0.5 )TiO 3 And (Bi) 0.5 Na 0.5 )TiO 3 The doping ratio in the composite positive electrode material was 3wt.%. The preparation method comprises the following steps:
(1) Nickel nitrate, manganese nitrate and magnesium nitrate (molar ratio 26:67:7) are added into deionized water to prepare a ternary metal salt solution with total metal ion concentration of 2 mol/L. Simultaneously preparing 2mol/L sodium hydroxide solution and 2mol/L ammonia water which are respectively used as a precipitator and a complexing agent.
(2) The temperature of the reaction kettle is raised to 40 ℃, ammonia water, sodium hydroxide solution and metal salt solution are slowly pumped into the reaction kettle at the flow rate of 50ml/min under the stirring rate of 300r/min until the D50 of the precipitated particles is 4.0 mu m, then the pumping speed of the metal salt solution is increased to 80ml/min until the D50 of the precipitated particles is 10.0 mu m, and the reaction is stopped.
(3) The precipitate was separated and washed by centrifugation with deionized water at 50 ℃ for 5 times.
(4) Dispersing the precipitate after centrifugal washing, putting the precipitate into a vacuum oven, and drying and dehydrating for 8 hours at 120 ℃ to obtain a positive electrode material precursor Ni 0.26 Mn 0.67 Mg 0.07 (OH) 2 Sealing and storing.
(5) Mixing the precursor of the positive electrode material and sodium peroxide according to the element molar ratio (Ni+Mn+Mg): na=1:0.67, then heating to 850 ℃ in a muffle furnace at a heating rate of 5 ℃/min, calcining for 12 hours, cooling, crushing and sieving to obtain the layered oxide positive electrode material.
(6) 485g of layered oxide cathode material and 15g (Bi 0.5 Na 0.5 )TiO 3 Transferring into a ball mill, adding a small amount of acetone, performing wet ball milling for 1h, transferring into a sintering furnace, heating to 600 ℃ at a speed of 3 ℃/min under the protection atmosphere of argon, maintaining the constant temperature for 20h, and naturally cooling to obtain Na 0.67 Ni 0.26 Mn 0.67 Mg 0.07 O 2 @ (Bi 0.5 Na 0.5 )TiO 3 A composite positive electrode material in which (Bi 0.5 Na 0.5 )TiO 3 The content was 3wt.%.
Example 3
The sodium ion battery positive electrode material for quick charge is prepared by the embodiment, is a composite positive electrode material with a core-shell structure, and a core layer is nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni 0.24 Mn 0.67 Mg 0.09 O 2 The shell layer material is (Bi) 0.5 Na 0.5 )TiO 3 And (Bi) 0.5 Na 0.5 )TiO 3 The doping ratio in the composite positive electrode material was 5wt.%. The preparation method comprises the following steps:
(1) Nickel sulfate, manganese sulfate and magnesium sulfate (molar ratio 24:67:9) are added into deionized water to prepare a ternary metal salt solution with total metal ion concentration of 1.5 mol/L. Simultaneously preparing 1.5mol/L sodium hydroxide solution and 2mol/L ammonia water which are respectively used as a precipitator and a complexing agent.
(2) The temperature of the reaction kettle is raised to 40 ℃, ammonia water, sodium hydroxide solution and metal salt solution are slowly pumped into the reaction kettle at the flow rate of 50ml/min under the stirring rate of 300r/min until the D50 of the precipitated particles is 4.0 mu m, then the pumping speed of the metal salt solution is increased to 80ml/min until the D50 of the precipitated particles is 10.0 mu m, and the reaction is stopped.
(3) The precipitate was separated and washed by centrifugation with deionized water at 50 ℃ for 5 times.
(4) Dispersing the precipitate after centrifugal washing, putting the precipitate into a vacuum oven, and drying and dehydrating for 8 hours at 120 ℃ to obtain a positive electrode material precursor Ni 0.24 Mn 0.67 Mg 0.09 (OH) 2 Sealing and storing.
(5) Mixing the precursor of the positive electrode material and sodium peroxide according to the element molar ratio (Ni+Mn+Mg): na=1:0.67, heating to 840 ℃ in a muffle furnace at a heating rate of 5 ℃/min, calcining for 14 hours, cooling, crushing and sieving to obtain the layered oxide positive electrode material.
(6) 475g of layered oxide cathode material and 25g (Bi 0.5 Na 0.5 )TiO 3 Transferring into a ball mill, adding a small amount of N-methyl pyrrolidone, performing wet ball milling for 1h, transferring into a sintering furnace, heating to 900 ℃ at a speed of 3 ℃/min under the condition of using argon as a protective atmosphere, maintaining the constant temperature for 20h, and naturally cooling to obtain Na 0.67 Ni 0.24 Mn 0.67 Mg 0.09 O 2 @ (Bi 0.5 Na 0.5 )TiO 3 A composite positive electrode material in which (Bi 0.5 Na 0.5 )TiO 3 The content was 5wt.%.
Comparative example 1
This comparative example is a nickel manganese-based layered oxide positive electrode material Na prepared according to the method of example 1 0.67 Ni 0.26 Mn 0.67 Mg 0.07 O 2 The outside of which is not coated (Bi 0.5 Na 0.5 )TiO 3 . The preparation method is described in the steps (1) - (5) of the example 1.
Comparative example 2
This comparative example is a piezoelectric ceramic (Bi 0.5 Na 0.5 )TiO 3 Replacement by equivalent amounts of ferroelectric piezoelectric ceramics Bi 4 Ti 3 O 12 The coating amount was also set to 1wt.%, and the preparation method was the same as in example 1, except that "5g (Bi) was used in the (6) th step 0.5 Na 0.5 )TiO 3 "replace with 5g ferroelectric piezoelectric ceramics Bi 4 Ti 3 O 12 。
Comparative example 3
This comparative example is a piezoelectric ceramic (Bi 0.5 Na 0.5 )TiO 3 The coating amount of (2) was increased to 9%, and the preparation method was the same as in example 1 except that "5g" (Bi) was added in the step (6) 0.5 Na 0.5 )TiO 3 45g of the total amount was added.
The positive electrode materials of the sodium ion batteries prepared in examples 1 to 3 and comparative examples 1 to 3 were assembled into button-type sodium ion batteries, respectively, and then subjected to electrical property tests, and the test results are shown in table 1.
The method for assembling the power buckle comprises the following steps: positive electrode material, conductive agent Super P and adhesive PVDF according to the mass ratio of 90:5:5 preparing the positive electrode material slurry by using a deaeration machineAfter the solid content of the slurry was adjusted to 39% by using N-methylpyrrolidone (NMP), the adjusted slurry was coated on an aluminum foil using an automatic coater (dry load amount was 3.6-3.7 g/cm) 2 ) And drying in a vacuum drying oven at 120 ℃, rolling by a roller press, and punching by a slicer to obtain the positive electrode plate. Then, a button 2032 battery was assembled in an argon glove box with water and oxygen content of less than 0.1ppm with the positive electrode sheet as the positive electrode and the sodium sheet as the negative electrode. NaPF with electrolyte of 1.5mol/L 6 Wherein the solvent is EC: PC: emc=1: 1:1 (volume ratio), 2wt.% FEC was additionally added and the separator was a glass fiber membrane GF/F. Constant current charge and discharge test is carried out on a blue electric battery test system in a constant temperature oven at 25 ℃, the voltage interval is 2.5-4.2V, the charge and discharge are carried out for 2 times at 10C, and the first-cycle charge and discharge capacity and the capacity retention rate after 200 cycles of 0.5C are tested.
The test results are shown in table 1 below.
Table 1:
the test data of the button cell in the table 1 show that the button cell prepared by the scheme has high button capacity, the specific capacity of 10C reaches more than 106mAh/g, and the capacity retention rate of 200 times under the current density of 0.5C is more than 90%.
As can be seen from the comparison of examples 1-3 and comparative example 1, compared with the nickel-manganese-based layered oxide cathode material which is not coated by BNT, the capacity exertion, the rate capability and the cycle stability of the composite cathode material prepared by BNT coating are improved; as is clear from the comparison of examples 1 to 3 and comparative example 2, when the piezoelectric ceramic (Bi 0.5 Na 0.5 )TiO 3 After being replaced by other ferroelectric piezoelectric ceramics, the multiplying power performance and the cycling stability of the anode material are reduced; as is evident from the comparison of examples 1 to 3 and comparative example 3, when the BNT amount as a coating material is too high, the rate performance and cycle stability of the cathode material are lowered. Thus, the invention provides Na 0.67 Ni x Mn y Mg z O 2 The composite positive electrode material of the BNT sodium ion battery has excellent rate performance and cycle stability.
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 same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (10)
1. A preparation method of a sodium ion battery positive electrode material capable of being used for quick charge is characterized in that the material is a composite positive electrode material with a core-shell structure, and a core layer is nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x+y+z=1; the shell layer material is (Bi) 0.5 Na 0.5 )TiO 3 And (Bi) 0.5 Na 0.5 )TiO 3 The doping proportion in the composite positive electrode material is 1-5wt.%; the preparation method of the sodium ion positive electrode material comprises the following steps:
s1, preparing a metal salt solution, wherein the metal salt solution contains nickel, manganese and magnesium metal ions, pumping the metal salt solution, a complexing agent solution and a precipitant solution into a reactor at the same time for coprecipitation reaction, washing a precipitated product after the reaction is finished, and drying to obtain a positive electrode material precursor;
s2, mixing and calcining the positive electrode material precursor and a sodium compound, cooling to room temperature, crushing and sieving to obtain a nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 Wherein x is more than 0 and less than 1, y is more than 0 and less than 1, z is more than 0 and less than 1, and x+y+z=1;
s3, preparing nickel-manganese-based layered oxide anode material Na 0.67 Ni x Mn y Mg z O 2 Mixing with BNT under the existence of solvent, wet ball milling, suction filtering, sintering and solid solution reacting to obtain composite anodeMaterial Na 0.67 Ni x Mn y Mg z O 2 BNT coated on nickel-manganese-based layered oxide positive electrode material Na 0.67 Ni x Mn y Mg z O 2 And an exterior.
2. The method for preparing a positive electrode material for a sodium ion battery according to claim 1, wherein x=0.24 to 0.28, y=0.67, and z=0.05 to 0.09.
3. The method for preparing a positive electrode material of a sodium ion battery for quick charge according to claim 1, wherein in S1, raw materials used for preparing the metal salt solution include nickel salt, manganese salt and magnesium salt, and the nickel salt is at least one of sulfate, nitrate and halogen salt of nickel; the manganese salt is at least one of sulfate, nitrate and halogen salt of manganese; the magnesium salt is at least one of sulfate, nitrate and halogen salt of magnesium.
4. The method for preparing a positive electrode material for a sodium ion battery according to claim 1, wherein in S1, the total concentration of metal ions in the metal salt solution is 0.5 to 2M.
5. The method for preparing a positive electrode material for a sodium ion battery, which can be used for quick charge according to claim 1, wherein in S1, the complexing agent solution is ammonia water, and the precipitant solution is sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
6. The method for preparing a positive electrode material for a sodium ion battery according to claim 5, wherein in S1, the reactor is preheated and heated, stirring of the reactor is started at a speed of 200-350rpm, then ammonia water, a precipitant solution and a metal salt solution are pumped into the reaction kettle at a slow speed, the particle size of the product particles is observed, the pumping speed of the metal salt solution is increased until the particle size D50 of the product particles is 4.0 μm, the particle size D50 of the product particles is 10.0 μm, and the pumping of the metal salt solution is stopped, thereby completing the reaction.
7. The method for preparing a positive electrode material for a fast-charging sodium ion battery according to claim 1, wherein in S2, the sodium compound is at least one of sodium carbonate, sodium hydroxide, sodium oxide, sodium peroxide, sodium phosphate, sodium sulfate, sodium dihydrogen phosphate, sodium dihydrogen sulfate and sodium phenolate.
8. The method for preparing a positive electrode material for a fast-charging sodium ion battery according to claim 1, wherein in S2, the conditions of the calcination treatment are: heating to 600-1050 ℃ at a heating rate of 3-10 ℃/min, and calcining for 5-36h; calcination is carried out in an atmosphere of air, oxygen or argon;
in S3, sintering conditions are as follows: heating to 500-950 ℃ at a heating rate of 3-10 ℃/min, calcining for 5-36h, and using argon as a protective atmosphere in the sintering process.
9. The method for preparing the positive electrode material of the sodium ion battery, which can be used for quick charge, according to claim 1, wherein the solvent used for wet ball milling is at least one of water, ethanol, N-methylpyrrolidone and acetone; the ball milling time is 1-3h.
10. A sodium ion battery positive electrode material useful for rapid charging, which is produced by the production method of any one of claims 1 to 9.
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