CN117658238A - Double-phase sodium ion battery positive electrode material and preparation method and application thereof - Google Patents
Double-phase sodium ion battery positive electrode material and preparation method and application thereof Download PDFInfo
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- CN117658238A CN117658238A CN202311660184.XA CN202311660184A CN117658238A CN 117658238 A CN117658238 A CN 117658238A CN 202311660184 A CN202311660184 A CN 202311660184A CN 117658238 A CN117658238 A CN 117658238A
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- ion battery
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000007774 positive electrode material Substances 0.000 title claims description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 239000011734 sodium Substances 0.000 claims abstract description 26
- 238000000975 co-precipitation Methods 0.000 claims abstract description 25
- IREHHCMIJCTSKK-UHFFFAOYSA-H [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] Chemical compound [OH-].[Fe+2].[Mn+2].[Ni+2].[OH-].[OH-].[OH-].[OH-].[OH-] IREHHCMIJCTSKK-UHFFFAOYSA-H 0.000 claims abstract description 22
- 239000010405 anode material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 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 17
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 10
- 150000002696 manganese Chemical class 0.000 claims abstract description 10
- 150000002815 nickel Chemical class 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 6
- 230000001681 protective effect Effects 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 13
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 239000011572 manganese Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 5
- 230000002431 foraging effect Effects 0.000 claims description 5
- 229910001437 manganese ion Inorganic materials 0.000 claims description 5
- 229910001453 nickel ion Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 4
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 4
- 239000011790 ferrous sulphate Substances 0.000 claims description 4
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 4
- 239000011565 manganese chloride Substances 0.000 claims description 4
- 235000002867 manganese chloride Nutrition 0.000 claims description 4
- 229940099607 manganese chloride Drugs 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- 239000012670 alkaline solution Substances 0.000 claims description 3
- 229960002089 ferrous chloride Drugs 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 238000010348 incorporation Methods 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 4
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 230000002051 biphasic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical group [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 125000001153 fluoro group Chemical group F* 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015556 catabolic process Effects 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
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000003631 expected effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011812 mixed powder Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000007704 transition Effects 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)
Abstract
The invention discloses a double-phase sodium ion battery anode material and a preparation method and application thereof. The preparation method comprises the following steps: (1) Preparing a mixed salt solution by using nickel salt, ferrous salt and manganese salt; (2) Under the atmosphere of protective gas, adding the mixed salt solution, the alkali solution and the ammonia water into a reaction container for coprecipitation reaction to obtain a nickel-iron-manganese hydroxide precursor; (3) And mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF, and calcining to obtain the double-phase sodium ion battery anode material. According to the method, the P2/O3 mixed phase can be constructed by adopting LiF to carry out metal and nonmetal simultaneous double doping on the nickel-iron-manganese hydroxide precursor, so that the circulation stability and the low-temperature performance are improved.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, and relates to a double-phase sodium ion battery positive electrode material, a preparation method and application thereof.
Background
P2 and O3 layered oxide anodes are easily synthesized and widely studied, wherein P2 type anodes have good rate capability and cycle life, while O3 type anode materials exhibit higher initial capacities. However, these layered structures all exhibit multiple phase changes and capacity degradation during long-term cycling. The combination of phases, adjustment of metal components, and combination of structure-stabilizing elements are effective modification means. In recent years, by controlling the reaction conditions, doping elements such as Li, mg, al, ti, mn, co, fe, etc., a synergistic effect of the bipolar positive electrode can be synthesized, and electrochemical performance has been improved.
CN116470034a discloses a preparation method of a positive electrode material with a dual-phase composite structure of a sodium ion battery, which forms a spinel phase by performing surface structure regulation and control on an O3 phase, uses a spinel type ferrite compound with three-dimensional ion diffusion characteristics as a coating material to perform surface modification, and builds an ion transmission channel between a body and two phases of the coating; and forming the VO filled with hetero atoms in situ in the ferrite, and finally forming the surface modification film layer with good ion transmission and electron conduction capability.
CN116207359a discloses a high entropy positive electrode material sodium ion battery with adjustable biphase proportion and a preparation method thereof, the preparation method comprises: s1: mixing a sodium source, an iron source, a cobalt source, a nickel source, a manganese source and a titanium source according to the element composition of the positive electrode material of the sodium ion battery, replacing the titanium part with copper in an equimolar manner, and fully ball-milling to obtain a mixed powder sample; s2: mixing according to the regulated element composition of the anode material; s3: tabletting a raw material mixture sample, sintering at a high temperature, and cooling to room temperature; s4: mixing the anode material with a conductive additive and polyvinylidene fluoride, and adding an N-methyl pyrrolidone solvent; s5: and assembling the prepared positive plate and the metal sodium plate negative electrode into the sodium ion battery. The patent can realize the adjustment of the proportion of the P2/O3 phase of the positive electrode material of the sodium ion battery by only partially replacing the titanium element with the copper element, improves the specific capacity of the positive electrode material, has high specific capacity, and is easy to realize mass production.
However, the current research on the positive electrode material of sodium ion battery mainly focuses on the normal temperature range, while Na at the temperature below zero + The diffusion process is slow, and the specific capacity and the rate capability are greatly reduced along with the transition from room temperature to low temperature.
Therefore, providing a high-performance positive electrode material of a sodium ion battery, which has good low-temperature performance, is a technical problem to be solved at present.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a double-phase sodium ion battery anode material and a preparation method and application thereof.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a second aspect, the invention provides a preparation method of a bipolar sodium ion battery anode material, which is characterized by comprising the following steps:
(1) Preparing a mixed salt solution by using nickel salt, ferrous salt and manganese salt;
(2) Under the atmosphere of protective gas, adding the mixed salt solution, the alkali solution and the ammonia water into a reaction container for coprecipitation reaction to obtain a nickel-iron-manganese hydroxide precursor;
(3) And mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF, and calcining to obtain the double-phase sodium ion battery anode material.
The method of the invention can construct P2/O3 mixture by adopting LiF to carry out simultaneous double doping of metal and nonmetal on the nickel-iron-manganese hydroxide precursorIn the positive electrode material, the doping of lithium can change the valence state of manganese element (from trivalent oxidation to tetravalent oxidation), so as to inhibit the ginger-Taylor effect; fluorine substitution can effectively solve the problem of oxygen loss in sodium-based transition metal oxides to improve cycle stability. In addition, F ions with stronger electronegativity are doped to form TM-F bonds with stronger binding force, which can reduce TMO 2 The sliding of the layers makes the layered structure more stable. At the same time, facilitate faster Na + Transfer kinetics and improves sodium storage at low temperatures. Compared with the P2 and O3 single-phase positive electrode material, the double-phase sodium ion battery positive electrode material prepared by the method has a more stable sodium ion transmission channel, and improves the circulation stability and the low-temperature performance.
In the preparation method, the co-doping of Li and F is carried out by adopting a one-step method in the calcination stage, so that the preparation process is simplified, the production efficiency is improved, and the production cost is reduced.
The kind of the shielding gas is not particularly limited in the present invention, and may be any one or a combination of at least two of nitrogen and inert gas. The inert gas may be helium, argon, or the like.
Preferably, the nickel salt of step (1) comprises at least one of nickel chloride, nickel sulfate and nickel nitrate.
Preferably, the ferrous salt of step (1) comprises at least one of ferrous chloride, ferrous sulfate and ferrous nitrate.
Preferably, the manganese salt of step (1) comprises at least one of manganese chloride, manganese sulfate and manganese nitrate.
Preferably, the total concentration of nickel ions, ferrous ions and manganese ions in the mixed salt solution of step (1) is 1mol/L to 3mol/L, for example 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or 3mol/L, etc.
Preferably, the alkaline solution of step (2) comprises at least one of sodium hydroxide, sodium carbonate and potassium hydroxide.
Preferably, the concentration of the alkaline solution in step (2) is 3mol/L to 5mol/L, for example 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L, 5mol/L or the like.
Preferably, the concentration of the aqueous ammonia in the step (2) is 8mol/L to 12mol/L, for example 8mol/L, 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L, 10.5mol/L, 11mol/L or 12mol/L, etc.
Preferably, the temperature of the coprecipitation reaction in step (2) is 40 to 70 ℃, for example 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, or the like.
Preferably, the pH of the coprecipitation reaction of step (2) is 9 to 11.5, for example 9, 9.5, 10, 10.5, 11 or 11.5, etc.
Preferably, the co-precipitation reaction of step (2) is accompanied by stirring at a speed of 150rpm to 350rpm, for example 150rpm, 170rpm, 180rpm, 200rpm, 220rpm, 240rpm, 260rpm, 280rpm, 300rpm, 325rpm or 350rpm, etc.
Preferably, the time of the coprecipitation reaction in step (2) is 60 to 100 hours, for example 60, 62, 65, 68, 70, 75, 78, 80, 85, 88, 90, 95 or 100 hours, etc.
As a preferable technical scheme of the preparation method of the bipolar sodium ion battery anode material, the addition amount of LiF in the step (3) meets the following conditions: 0.02mol% to 0.2mol% of Li element is doped into 1mol of the positive electrode material. The amount of the incorporated molar amount is, for example, 0.02mol%, 0.04mol%, 0.05mol%, 0.07mol%, 0.08mol%, 0.1mol%, 0.12mol%, 0.15mol%, 0.17mol%, or 0.2 mol%.
Preferably, the molar amount of LiF is 1.05 times the Li element incorporation amount.
Preferably, the temperature of the calcination in step (3) is 800 to 1000 ℃, for example 800 ℃, 825 ℃, 850 ℃, 875 ℃, 900 ℃, 920 ℃, 950 ℃, 975 ℃, or 1000 ℃, etc.
Preferably, the calcination in step (3) is carried out for a period of time ranging from 10h to 15h, for example 10h, 10.5h, 11h, 11.5h, 12h, 12.5h, 13h, 13.5h, 14h, 14.5h or 15h, etc.
As a preferable technical scheme of the preparation method of the bipolar sodium ion battery anode material, the preparation method comprises the following steps:
step 1, fully mixing nickel salt, ferrous salt and manganese salt according to the formula amount to prepare mixed salt solution;
step 2, in the atmosphere of inert gas, respectively adding the mixed salt solution, the alkali solution and the ammonia water in the step 1 into a reaction kettle through a metering pump, and stirring to perform coprecipitation reaction;
step 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle into an aging tank for aging, and then centrifuging, washing and drying to obtain a nickel-iron-manganese hydroxide precursor;
step 4, mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF, and calcining at 800-1000 ℃ for 10-15 h to obtain the double-phase sodium ion battery anode material;
wherein, the ratio of the molar quantity of LiF to the total molar quantity of nickel, iron and manganese elements is 0.021-0.21, and the molar quantity of sodium source is 5% excess on the basis of the molar formula quantity.
In a second aspect, the invention provides a bipolar sodium ion battery positive electrode material prepared by the preparation method in the first aspect, wherein the bipolar sodium ion battery positive electrode material is provided with a P3/O3 mixed phase.
Preferably, the chemical formula of the positive electrode material of the double-phase sodium-ion battery is Na 0.67 Li x Ni a Mn b Fe c O 2 F 2-y Wherein x is more than or equal to 0.02 and less than or equal to 0.2,0<y<2，a+b+c＝1。
The double-phase sodium ion battery anode material prepared by the preparation method provided by the invention has good cycle performance and low-temperature performance.
The following preferred technical solutions are used as the present invention, but not as limitations on the technical solutions provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solutions.
Preferably, a: b: c=1:1:1.
Preferably, the average particle size of the bipolar sodium ion battery positive electrode material is 5 μm to 15 μm, for example 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 12 μm, 13 μm or 15 μm, etc.
In a third aspect, the present invention provides a sodium ion battery comprising the bipolar sodium ion battery positive electrode material according to the first aspect.
The sodium ion battery assembled by the double-phase sodium ion battery anode material has good cycle performance and low-temperature performance.
The numerical ranges recited herein include not only the recited point values, but also any point values between the recited numerical ranges that are not recited, and are limited to, and for the sake of brevity, the invention is not intended to be exhaustive of the specific point values that the recited range includes.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method, the P2/O3 mixed phase can be constructed by adopting LiF to carry out metal and nonmetal simultaneous double doping on the nickel-iron-manganese hydroxide precursor, and the doping of lithium in the positive electrode material can change the valence state of manganese element (from trivalent oxidation to tetravalent oxidation), so that the ginger-Taylor effect is inhibited; fluorine substitution can effectively solve the problem of oxygen loss in sodium-based transition metal oxides to improve cycle stability. In addition, F ions with stronger electronegativity are doped to form TM-F bonds with stronger binding force, which can reduce the sliding of the TMO2 layer, thereby leading the layered structure to be more stable. At the same time, faster Na+ transfer kinetics are facilitated and sodium storage at low temperatures is improved. Compared with the P2 and O3 single-phase positive electrode material, the double-phase sodium ion battery positive electrode material prepared by the method has a more stable sodium ion transmission channel, and improves the circulation stability and the low-temperature performance.
(2) In the preparation method, the co-doping of Li and F is carried out by adopting a one-step method in the calcination stage, so that the preparation process is simplified, the production efficiency is improved, and the production cost is reduced.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments.
Example 1
The embodiment provides a preparation method of a bipolar sodium ion battery anode material, which comprises the following steps:
step 1, fully mixing nickel salt (nickel nitrate), ferrous salt (ferrous sulfate) and manganese salt (manganese chloride) according to a molar ratio of 1:1:1 to prepare a mixed salt solution, wherein the total concentration of nickel ions, ferrous ions and manganese ions is 2mol/L;
step 2, in an argon atmosphere, adding the mixed salt solution, the alkali solution (3 mol/L NaOH solution) and 10mol/L ammonia water in the step 1 into a reaction kettle through a metering pump respectively, stirring at a speed of 200rpm, and performing coprecipitation reaction, wherein the temperature of the coprecipitation reaction is 50 ℃, the pH of the coprecipitation reaction is controlled at 9.5, and the time of the coprecipitation reaction is 65 hours;
step 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches 10 mu m, transferring the materials in the reaction kettle into an aging tank for aging, and then centrifuging, washing and drying to obtain a nickel-iron-manganese hydroxide precursor;
and 4, mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF according to a molar ratio of 1:0.7035:0.105, and calcining at 900 ℃ for 12 hours to obtain the double-phase sodium ion battery anode material.
The chemical formula of the positive electrode material of the biphasic sodium ion battery prepared in the embodiment is Na 0.67 Li 0.1 Ni 0.33 Mn 0.33 Fe 0.33 O 2 F 2-y Wherein 2-y<0.1, and the average particle diameter was 10. Mu.m.
Example 2
The embodiment provides a preparation method of a bipolar sodium ion battery anode material, which comprises the following steps:
step 1, fully mixing nickel salt (nickel sulfate), ferrous salt (ferrous sulfate) and manganese salt (manganese sulfate) according to a molar ratio of 1:1:1 to prepare a mixed salt solution, wherein the total concentration of nickel ions, ferrous ions and manganese ions is 3mol/L;
step 2, in helium atmosphere, adding the mixed salt solution, the alkali solution (5 mol/L KOH solution) and 12mol/L ammonia water in the step 1 into a reaction kettle through a metering pump respectively, stirring at a speed of 350rpm, performing coprecipitation reaction, wherein the temperature of the coprecipitation reaction is 65 ℃, the pH of the coprecipitation reaction is controlled at 11.0, and the time of the coprecipitation reaction is 80 hours;
step 3, when the granularity of the precursor particles in the reaction kettle reaches 10 mu m, stopping the reaction, transferring the materials in the reaction kettle into an aging tank for aging, and then centrifuging, washing and drying to obtain a nickel-iron-manganese hydroxide precursor;
and 4, mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF according to a molar ratio of 1:0.7035:0.0525, and calcining at 800 ℃ for 15 hours to obtain the double-phase sodium-ion battery anode material.
The chemical formula of the positive electrode material of the biphasic sodium ion battery prepared in the embodiment is Na 0.67 Li 0.05 Ni 0.33 Mn 0.3 3 Fe 0.33 O 2 F 2-y Wherein 2-y<0.05, and the average particle diameter was 10. Mu.m.
Example 3
The embodiment provides a preparation method of a bipolar sodium ion battery anode material, which comprises the following steps:
step 1, fully mixing nickel salt (nickel chloride), ferrous salt (ferrous chloride) and manganese salt (manganese chloride) according to a molar ratio of 1:1:1 to prepare a mixed salt solution, wherein the total concentration of nickel ions, ferrous ions and manganese ions is 1mol/L;
step 2, in an argon atmosphere, adding the mixed salt solution, the alkali solution (4 mol/L NaOH solution) and 8mol/L ammonia water in the step 1 into a reaction kettle through a metering pump respectively, stirring at a speed of 150rpm, and performing coprecipitation reaction, wherein the temperature of the coprecipitation reaction is 40 ℃, the pH of the coprecipitation reaction is controlled to be 10.5, and the time of the coprecipitation reaction is 100 hours;
step 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches 10 mu m, transferring the materials in the reaction kettle into an aging tank for aging, and then centrifuging, washing and drying to obtain a nickel-iron-manganese hydroxide precursor;
and 4, mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF according to a molar ratio of 1:0.7035:0.1575, and calcining at 1000 ℃ for 10 hours to obtain the bipolar sodium ion battery anode material.
The chemical formula of the positive electrode material of the biphasic sodium ion battery prepared in the embodiment is Na 0.67 Li 0.15 Ni 0.33 Mn 0.3 3 Fe 0.33 O 2 F 2-y ，2-y<0.15, and the average particle diameter was 10. Mu.m.
Example 4
The present example provides a method for preparing a bipolar sodium ion battery cathode material, which is different from example 1 in that the addition amount of LiF is changed so that the molar ratio of the nickel-iron-manganese hydroxide precursor to LiF is 1:0.00525.
The chemical formula of the positive electrode material of the biphasic sodium ion battery prepared in the embodiment is Na 0.67 Li 0.005 Ni 0.33 Mn 0.3 3 Fe 0.33 O 2 F 2-y Wherein 2-y<0.005, and the average particle diameter was 10. Mu.m.
Example 5
The present example provides a method for preparing a bipolar sodium ion battery cathode material, which is different from example 1 in that the addition amount of LiF is changed so that the molar ratio of the nickel-iron-manganese hydroxide precursor to LiF is 1:0.315.
The chemical formula of the positive electrode material of the biphasic sodium ion battery prepared in the embodiment is Na 0.67 Li 0.3 Ni 0.33 Mn 0.33 Fe 0.33 O 2 F 2-y ，2-y<0.3, the average particle diameter was 10. Mu.m.
Comparative example 1
This comparative example provides a method for preparing a positive electrode material for a sodium ion battery, which is different from example 1 in that LiF is replaced with NaF and LiOH, and the contents of Li and F in the positive electrode material for a sodium ion battery prepared in this comparative example are the same as example 1.
Performance test:
at the temperature of minus 25 ℃, the prepared positive electrode material is used as a positive electrode main material to prepare a positive electrode (wherein the mass ratio of the positive electrode main material to super P to PVDF is 8:1:1), a metal sodium sheet is used as a negative electrode to be assembled into a CR2032 button cell, and then electrochemical performance tests are carried out under the voltage window of 2.5-4.35V, the ratio performance and the capacity retention rate of the button cell at 0.05C/0.1C/0.15C/0.2C, and the results of the button cell cycling for 85 circles under the temperature of 0.1C are shown in Table 1.
TABLE 1
As can be seen from Table 1, the method of the invention can construct P2/O3 mixed phase by adopting LiF to carry out metal and nonmetal simultaneous double doping on the nickel-iron-manganese hydroxide precursor, thereby improving the cycle stability and the low temperature performance. In comparative example 1, li and F are provided by two substances, respectively, the process flow is complicated, the kinds of raw materials become large, the mixing degree becomes low, and finally the uniformity of doping is affected.
As is clear from comparison of examples 1 and 4 to 5, the preferred range of the addition amount of LiF is present, and if the addition amount of LiF is too small, the effect on the overall internal electronic structure of the crystal is small, the expected effect cannot be exerted, and the doping effect cannot be achieved; if the LiF is used too much, the proportion of ternary metal is reduced too much, the capacity is reduced drastically, more serious lattice distortion is caused, the material structure is collapsed, and the performance is invalid.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. The preparation method of the bipolar sodium ion battery anode material is characterized by comprising the following steps of:
(1) Preparing a mixed salt solution by using nickel salt, ferrous salt and manganese salt;
(2) Under the atmosphere of protective gas, adding the mixed salt solution, the alkali solution and the ammonia water into a reaction container for coprecipitation reaction to obtain a nickel-iron-manganese hydroxide precursor;
(3) And mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF, and calcining to obtain the double-phase sodium ion battery anode material.
2. The method for preparing a bipolar sodium ion battery positive electrode material according to claim 1, wherein the nickel salt in the step (1) comprises at least one of nickel chloride, nickel sulfate and nickel nitrate;
preferably, the ferrous salt of step (1) comprises at least one of ferrous chloride, ferrous sulfate and ferrous nitrate;
preferably, the manganese salt of step (1) comprises at least one of manganese chloride, manganese sulfate and manganese nitrate;
preferably, in the mixed salt solution in the step (1), the total concentration of nickel ions, ferrous ions and manganese ions is 1mol/L to 3mol/L;
preferably, the alkaline solution of step (2) comprises at least one of sodium hydroxide, sodium carbonate and potassium hydroxide;
preferably, the concentration of the alkali solution in the step (2) is 3mol/L to 5mol/L;
preferably, the concentration of the ammonia water in the step (2) is 8mol/L to 12mol/L.
3. The method for preparing a bipolar sodium ion battery positive electrode material according to claim 1 or 2, wherein the temperature of the coprecipitation reaction in the step (2) is 40-70 ℃;
preferably, the pH of the coprecipitation reaction in step (2) is 9 to 11.5;
preferably, stirring is carried out during the coprecipitation reaction in the step (2), and the stirring speed is 150 rpm-350 rpm;
preferably, the time of the coprecipitation reaction in the step (2) is 60-100 hours.
4. The method for preparing a bipolar sodium ion battery positive electrode material according to any one of claims 1 to 3, wherein the LiF added in the step (3) is added in an amount such that: doping 0.02mol% to 0.2mol% of Li element into 1mol of positive electrode material;
preferably, the molar amount of LiF is 1.05 times the Li element incorporation amount.
5. The method for preparing a bipolar sodium ion battery positive electrode material according to any one of claims 1 to 4, wherein the calcining temperature in step (3) is 800 ℃ to 1000 ℃;
preferably, the calcination in step (3) takes 10 to 15 hours.
6. The method for preparing a bipolar sodium ion battery positive electrode material according to any one of claims 1-5, wherein the method comprises the steps of:
step 1, fully mixing nickel salt, ferrous salt and manganese salt according to the formula amount to prepare mixed salt solution;
step 2, in the atmosphere of inert gas, respectively adding the mixed salt solution, the alkali solution and the ammonia water in the step 1 into a reaction kettle through a metering pump, and stirring to perform coprecipitation reaction;
step 3, stopping the reaction when the granularity of the precursor particles in the reaction kettle reaches the required size, transferring the materials in the reaction kettle into an aging tank for aging, and then centrifuging, washing and drying to obtain a nickel-iron-manganese hydroxide precursor;
step 4, mixing the nickel-iron-manganese hydroxide precursor, a sodium source and LiF, and calcining at 800-1000 ℃ for 10-15 h to obtain the double-phase sodium ion battery anode material;
wherein, the ratio of the molar quantity of LiF to the total molar quantity of nickel, iron and manganese elements is 0.021-0.21, and the molar quantity of sodium source is 5% excess on the basis of the molar formula quantity.
7. A dual-phase sodium ion battery positive electrode material prepared by the preparation method according to any one of claims 1 to 6, wherein the dual-phase sodium ion battery positive electrode material has a P3/O3 mixed phase therein;
preferably, the two phasesThe chemical formula of the positive electrode material of the sodium ion battery is Na 0.67 Li x Ni a Mn b Fe c O 2 F 2-y Wherein x is more than or equal to 0.02 and less than or equal to 0.2,0<y<2，a+b+c＝1。
8. The bipolar sodium ion battery positive electrode material of claim 7 wherein a: b: c = 1:1:1.
9. The bipolar sodium ion battery positive electrode material of claim 7 or 8, wherein the average particle size of the bipolar sodium ion battery positive electrode material is 5-15 μm.
10. A sodium ion battery, characterized in that the sodium ion battery comprises the bipolar sodium ion battery positive electrode material according to any one of claims 7-9.
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