CN116093305A - Li (lithium ion battery) + Substituted sodium ion battery anode material, preparation method and application - Google Patents
Li (lithium ion battery) + Substituted sodium ion battery anode material, preparation method and application Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 88
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical class [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 title claims description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 title claims description 11
- 239000011734 sodium Substances 0.000 claims abstract description 68
- 239000007774 positive electrode material Substances 0.000 claims abstract description 45
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 239000000203 mixture Substances 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 14
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000003825 pressing Methods 0.000 claims abstract description 9
- 238000005303 weighing Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 19
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 17
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000008859 change Effects 0.000 abstract description 6
- 239000002131 composite material Substances 0.000 abstract description 2
- 230000036961 partial effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 19
- 239000011149 active material Substances 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 16
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 239000002033 PVDF binder Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 239000011888 foil Substances 0.000 description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 10
- 230000002441 reversible effect Effects 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 8
- 229910021385 hard carbon Inorganic materials 0.000 description 8
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 8
- 230000007704 transition Effects 0.000 description 8
- 238000009792 diffusion process Methods 0.000 description 7
- 239000003365 glass fiber Substances 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 238000000634 powder X-ray diffraction Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 238000006467 substitution reaction Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- 238000001238 wet grinding Methods 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 102000004310 Ion Channels Human genes 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Complex oxides containing nickel and at least one other metal element
- C01G53/42—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2
- C01G53/44—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/50—Complex oxides containing nickel and at least one other metal element containing alkali metals, e.g. LiNiO2 containing manganese of the type (MnO2)n-, e.g. Li(NixMn1-x)O2 or Li(MyNixMn1-x-y)O2
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- 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
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- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- 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
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- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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Abstract
The invention provides Li + The substituted sodium ion battery positive electrode material comprises layered metal oxide, and the chemical composition of the layered metal oxide is as follows: na (Na) 0.766+x Li x Ni 0.33‑ x Mn 0.5 Fe 0.1 Ti 0.07 O 2 Wherein 0 is<x is less than or equal to 0.1. The preparation method comprises the following steps: weighing and uniformly mixing the raw materials according to the molar ratio x (0.33-x) of 0.5:0.1:0.07 (0.766+x); transferring into a ball milling tank, adding ethanol as a ball milling medium for ball milling, and drying to obtain a precursorA powder; pressing the precursor powder into a sheet, and calcining in an air atmosphere to obtain Li + Substituted sodium ion battery positive electrode materials. The method is carried out by partial Li + For Ni 2+ Can inhibit the problems of unstable structure and non-ideal electrochemical performance caused by high-voltage phase change. The composite material can be applied to sodium ion batteries, and the comprehensive performance can be improved.
Description
Technical Field
The invention relates to the field of battery anode materials, in particular to a lithium ion battery anode material + Substitution inhibiting high-voltage phase change sodium ion battery anode material, and preparation method and application thereof.
Background
Development and development of clean and sustainable energy is an important research topic. At present, the lithium ion battery is widely applied to the fields of portable electronic equipment, electric automobiles and large-scale energy storage due to the advantages of high energy density, stable cycle performance, long service life and the like. However, because of the problems of lithium resource shortage, great exploitation difficulty and the like, the cost of lithium salt increases year by year, so that development of a novel low-cost and alternative electrochemical energy storage technology is urgent. The storage is rich (2.3-2.8%), the cost is lower (Na) 2 CO 3 The cost is lower than Li 2 CO 3 About 20-30 times), and sodium ion batteries with similar physicochemical properties and working principles as lithium, have great alternative potential, and are expected to play an important role in large-scale energy storage systems in the future.
In the positive electrode material of the sodium ion battery, the layered oxide has simple preparation method and two-dimensional Na + The characteristics of diffusion channel, high specific capacity, strong moldability, etc. are of great interest. The sodium ion coordination environment and the stacking sequence of the transition metal layer and the oxygen layer are classified into O-type and P-type. The P-type layered oxide shows better multiplying power performance due to a wider ion channel, while the O-type layered oxide has higher theoretical capacity and great potential in practical application. However, complicated phase changes and large diffusion barriers during the reaction process lead to the problems of irreversible phase changes, rapid capacity decay and the like.
Through ion doping/substitution, the phase components can be effectively regulated and controlled, the complex phase change is inhibited, and Na is improved + Diffusion rate, and improved electrochemical stability. Therefore, a proper modification strategy is selected, and the method has very important significance for developing a novel sodium ion battery with environmental protection, stable structure, proper electrochemical platform and large specific capacity。
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide Li + Substitution inhibiting high-voltage phase change sodium ion battery anode material, and preparation method and application thereof. The invention is implemented by part of Li + For Ni 2+ Not only can realize controllable conversion of P2 to O3 phase, but also can effectively inhibit Na + Vacancy ordering and transition metal layer induced phase transition slip (P3-O3') in high voltage region to improve Na + The diffusion rate obviously improves the cycle stability and the multiplying power performance of the polymer, so as to inhibit the problems of unstable structure and non-ideal electrochemical performance caused by high-pressure phase change of the polymer. The whole preparation process is simple and efficient, has low cost, can improve the comprehensive performance when being applied to sodium ion batteries, and is easy for large-scale industrial production.
In order to achieve the above object, the technical scheme of the present invention is as follows.
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having a chemical composition of:
Na 0.766+x Li x Ni 0.33-x Mn 0.5 Fe 0.1 Ti 0.07 O 2 wherein 0 is<x≤0.1。
Further, the value range of x is 0.04< x.ltoreq.0.1.
Further, the layered metal oxide is a P2/O3 phase oxide or an O3 phase oxide.
The invention provides Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
s1, respectively weighing a Li source, a Ni source, a Mn source, a Fe source, a Ti source and a Na source according to a molar ratio x (0.33-x) of 0.5:0.1:0.07 (0.766+x), wherein x is more than 0 and less than or equal to 0.1;
s2, uniformly mixing a Li source, a Ni source, a Fe source, a Mn source, ti and Na sources, transferring into a ball milling tank, adding ethanol as a ball milling medium for ball milling, and drying to obtain precursor powder;
s3, pressing the precursor powder into a sheet shape, and calcining in an air atmosphereFiring to obtain Li + Substituted sodium ion battery positive electrode materials.
Further, in S1, the Li source is Li 2 CO 3 The Ni source is NiO, and the Fe source is Fe 2 O 3 The Mn source is MnO 2 The Ti source is TiO 2 The Na source is Na 2 CO 3 . Purity of all powders>99％。
Further, in S2, the amount of ethanol added is 1 to 5% by weight based on the total mass of the precursor powder.
Further, in S2, the ball milling conditions are: the rotation speed of the ball milling process is 400r/min, and the time is 4h; the drying temperature was 80 ℃.
Further, in S3, the calcination conditions are: the calcination temperature is 900-950 ℃ and the calcination time is 10-15 h.
In S3, the precursor powder is pressed into a sheet at a pressure of 15 to 16MPa.
The invention provides Li + The application of the substituted sodium ion battery anode material in preparing sodium ion batteries.
The present invention provides a sodium ion battery comprising a Li as claimed in claim 1 + Substituted sodium ion battery positive electrode materials.
Further, the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and is assembled into a button battery in a glove box filled with inert atmosphere;
the counter electrode is a sodium sheet prepared from metal sodium; at least one side of the positive electrode sheet comprising Li as set forth in claim 1 + Substituted sodium ion battery positive electrode materials.
Further, the battery also comprises an electrolyte, wherein the electrolyte is prepared by mixing NaClO 4 Dissolving in Propylene Carbonate (PC) to form 1mol/L NaClO 4 Propylene Carbonate (PC) solution, and 5vol% fluoroethylene carbonate (FEC) was added.
Further, the separator is a glass fiber membrane (GF/D) from Whatman.
The invention has the beneficial effects that:
1. li provided by the invention + Substitution of sodium ion battery anode material Na for inhibiting high-voltage phase change 0.766+x Li x Ni 0.33- x Mn 0.5 Fe 0.1 Ti 0.07 O 2 Not only is environment-friendly and low in production cost, but also has excellent capacity, cycle stability and multiplying power characteristics.
2. The invention adopts a simple and easy preparation method and low-cost raw materials, and adopts part of Li + For Ni 2+ Is substituted to obtain a series of target Na-ion battery anode materials with different phase compositions and phase proportions 0.766+x Li x Ni 0.33- x Mn 0.5 Fe 0.1 Ti 0.07 O 2 . In order to maintain charge balance without changing the original valence state of the metal ion (Ni 2+ 、Mn 4+ 、Fe 3+ 、Ti 4+ ) The sodium content is correspondingly increased. Li (Li) + The partial substitution of the (C) successfully inhibits the phase transition of P3-O3' in a high-voltage area, so that the cycle stability and the multiplying power characteristic are obviously improved. The capacity retention rate of the modified positive electrode after 500 times of circulation at 5 ℃ is as high as 81.6%; after the full cell is assembled with hard carbon in a matching way, the full cell also shows excellent electrochemical performance. The layered metal oxide prepared by the method of the invention has excellent physical and chemical characteristics, can effectively regulate and control phase composition components and effectively inhibit Na + The vacancy ordering and transition metal layer causes phase transition slippage (P3-O3') in a high voltage area, and the phase transition metal layer is applied to a sodium ion battery, so that an effective solution is provided for the phase transition of the O3 type positive electrode material in the high voltage area, and the phase transition metal layer becomes a secondary energy storage device with extremely commercial competitiveness.
3. The reversible specific capacity and the working voltage of the sodium ion battery are respectively 138 mAh.g under the voltage interval of 2.2-4.3V -1 And 3.4V, an energy density of approximately 470 Wh.kg -1 。
4. The positive electrode of the sodium ion battery shows excellent multiplying power performance, and the capacity retention rate after 500 times of circulation at 5 ℃ is as high as 81.6%, thereby indicating that the electric diffusion rate of sodium ions is high.
Drawings
FIG. 1 is a P2/O3 type layered oxide obtained in comparative example 1
Na 0.766 Ni 0.33 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaNMFT) XRD pattern.
FIG. 2 is a P2/O3 type layered oxide obtained in example 1
Na 0.786 Li 0.02 Ni 0.31 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.02).
FIG. 3 is a P2/O3 type layered oxide obtained in example 2
Na 0.806 Li 0.04 Ni 0.29 Mn 0.5 Fe 0.1 Ti 0.07 O 2 XRD pattern of (NaLNMFT-0.04).
FIG. 4 shows the O3-type layered oxide obtained in example 3
Na 0.826 Li 0.06 Ni 0.27 Mn 0.5 Fe 0.1 Ti 0.07 O 2 XRD pattern of (NaLNMFT-0.06).
FIG. 5 shows the O3-type layered oxide obtained in example 4
Na 0.846 Li 0.08 Ni 0.25 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (nalmft-0.08).
FIG. 6 is a schematic diagram of an O3-type layered oxide obtained in example 5
Na 0.866 Li 0.1 Ni 0.23 Mn 0.5 Fe 0.1 Ti 0.07 O 2 XRD pattern of (NaLNMFT-0.1).
Fig. 7 is a charge-discharge curve at 0.2C of the positive electrode material obtained in comparative example 1.
Fig. 8 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 1.
Fig. 9 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 2.
Fig. 10 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 3.
Fig. 11 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 4.
Fig. 12 is a charge-discharge curve at 0.2C of the positive electrode material obtained in example 5.
Fig. 13 is a graph showing the cycle performance of the positive electrode materials obtained in examples 1 to 5 at 5C.
Fig. 14 is a charge-discharge curve at 1C for a full cell assembled in example 3 with hard carbon matching.
Fig. 15 is a graph of the cycling performance at 1C of a full cell assembled with a hard carbon match for example 3.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available unless otherwise specified.
Example 1
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having the chemical composition: na (Na) 0.78 6 Li 0.02 Ni 0.31 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.02)。
Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
respectively weighing 12.37mmol of Na according to stoichiometric ratio 2 CO 3 、9.3mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 、0.3mmol Li 2 CO 3 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 5% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.786 Li 0.02 Ni 0.31 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode is prepared by taking aluminum foil as a positive electrode current collector, taking a sodium ion battery positive electrode material as an active material, mixing the active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on the aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours. Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 2, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 2 show that the resulting cathode material consisted of 27.68% p2 phase and 72.32% o3 phase.
2. Electrochemical performance test
The assembled sodium ion battery is subjected to electrochemical performance in a voltage range of 2.2-4.3VTest (see fig. 8, fig. 13 and tables 1-3)). The results in fig. 8 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) is 116.8 mAh.g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles was 78.2%.
Example 2
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having the chemical composition: na (Na) 0.80 6 Li 0.04 Ni 0.29 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.04)。
Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
respectively weighing 12.69mmol Na according to stoichiometric ratio 2 CO 3 、8.7mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 、0.6mmol Li 2 CO 3 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 2% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.806 Li 0.04 Ni 0.29 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode is prepared by taking aluminum foil as a positive electrode current collector, taking a sodium ion battery positive electrode material as an active material, mixing the active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on the aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours.Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 3, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 3 show that the resulting cathode material consists of 1.8% p2 phase and 98.2% o3 phase.
2. Electrochemical performance test
The assembled sodium ion battery was subjected to electrochemical performance testing at a voltage interval of 2.2 to 4.3V (see fig. 9, 13 and tables 1-3)). The results in fig. 9 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) was 122.9mAh g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles was 82.7%.
Example 3
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having the chemical composition: na (Na) 0.82 6 Li 0.06 Ni 0.27 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.06)。
Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
respectively weighing 13.01mmol Na according to stoichiometric ratio 2 CO 3 、8.1mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 、0.9mmol Li 2 CO 3 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 2% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.826 Li 0.06 Ni 0.27 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode is prepared by taking aluminum foil as a positive electrode current collector, taking a sodium ion battery positive electrode material as an active material, mixing the active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on the aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours. Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 4, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 4 show that the resulting cathode material consists of 1.8% p2 phase and 98.2% o3 phase.
2. Electrochemical performance test
The assembled sodium ion battery was subjected to electrochemical performance testing at a voltage interval of 2.2 to 4.3V (see fig. 10, fig. 13 and tables 1-3)). The results in fig. 10 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (C) is 126.0 mAh.g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles is 81.6%.
Example 4
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having the chemical composition: na (Na) 0.84 6 Li 0.08 Ni 0.25 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.08)。
Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
respectively weighing 13.32mmol Na according to stoichiometric ratio 2 CO 3 、7.5mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 、1.2mmol Li 2 CO 3 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 2% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.846 Li 0.08 Ni 0.25 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode takes aluminum foil as a positive current collector, takes a positive material of a sodium ion battery as an active material,mixing an active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on an aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours to obtain the composite material. Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 5, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 5 show that the positive electrode material obtained was O3 phase.
2. Electrochemical performance test
The assembled sodium ion battery was subjected to electrochemical performance testing at a voltage interval of 2.2 to 4.3V (see fig. 11, fig. 13 and tables 1-3)). The results in fig. 11 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) is 118.1 mAh.g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles is 80.8%.
Example 5
Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having the chemical composition: na (Na) 0.86 6 Li 0.1 Ni 0.23 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT-0.1)。
Li + The preparation method of the substituted sodium ion battery anode material comprises the following steps:
in stoichiometric ratio13.64mmol Na was weighed out separately 2 CO 3 、6.9mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 、1.5mmol Li 2 CO 3 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 2% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.866 Li 0.1 Ni 0.23 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode is prepared by taking aluminum foil as a positive electrode current collector, taking a sodium ion battery positive electrode material as an active material, mixing the active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on the aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours. Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 6, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 6 show that the positive electrode material obtained was O3 phase.
2. Electrochemical performance test
The assembled sodium ion battery was subjected to electrochemical performance testing at a voltage interval of 2.2-4.3V (see fig. 12, 13 and tables 1-3). The results in fig. 12 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) is 118.7 mAh.g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles was 84.8%.
Comparative example 1
A sodium ion battery positive electrode material comprising a layered metal oxide having a chemical composition comprising: na (Na) 0.766 Ni 0.33 Mn 0.5 Fe 0.1 Ti 0.07 O 2 (NaLNMFT)。
The preparation method of the sodium ion battery anode material comprises the following steps:
respectively weighing 12.06mmol Na according to stoichiometric ratio 2 CO 3 、9.9mmol NiO、1.5mmol Fe 2 O 3 、15mmol MnO 2 、2.1mmol TiO 2 Placing in a ball milling tank, wherein Na 2 CO 3 5% excess to prevent volatilization losses during high temperature calcination.
Then adding 2% wt of absolute ethyl alcohol as a wet grinding solvent, ball-milling for 4 hours by using a planetary ball mill at a rotating speed of 450r/min, and then placing a ball-milling tank into an oven at 80 ℃ to dry the absolute ethyl alcohol, thereby obtaining uniformly mixed precursor powder.
Pressing the obtained precursor powder into small discs with the diameter of 12mm under the pressure of 16MPa, putting the small discs into a porcelain boat, transferring the small discs into a muffle furnace, calcining the small discs for 15h at the temperature of 950 ℃ in the air atmosphere, and cooling the small discs to the room temperature to obtain the sodium ion battery anode material Na 0.766 Ni 0.33 Mn 0.5 Fe 0.1 Ti 0.07 O 2 。
The working electrode was prepared as follows:
the working electrode takes aluminum foil as a positive current collector and takes a sodium ion battery positive material as a negative electrodeThe active material is prepared by mixing the active material, a conductive agent Super P and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, uniformly coating the mixture on an aluminum foil after size mixing, transferring the mixture into a vacuum drying oven, and drying the mixture at 80 ℃ for 10 hours. Wherein the diameter of the working electrode is 10mm, and the loading capacity of the active material is 2-3 mg cm -2 。
The sodium ion battery was prepared as follows:
the sodium ion battery comprises a negative electrode shell, a counter electrode, a diaphragm, a positive electrode plate, a gasket, a spring piece and a positive electrode shell, and a button battery with the model CR2032 is assembled in a glove box filled with inert atmosphere.
Wherein, a sodium sheet made of metallic sodium is used as a counter electrode; the electrolyte is NaClO with the concentration of 1mol/L 4 -Propylene Carbonate (PC) solution, and adding 5vol% fluoroethylene carbonate (FEC); the membrane is Whatman GF/D glass fiber membrane.
1. XRD analysis
The positive electrode material obtained above was subjected to an X-ray powder diffraction test to determine a phase, the test result is shown in fig. 1, and the XRD pattern was subjected to Rietveld by TOPAS software to determine a phase ratio. The results in fig. 1 show that the resulting cathode material consisted of 58.91% p2 phase and 41.09% o3 phase.
2. Electrochemical performance test
The assembled sodium ion battery was subjected to electrochemical performance testing at a voltage interval of 2.2 to 4.3V (see fig. 7, 13 and tables 1-3)). The results in fig. 7 show that at 0.2C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) is 114.4 mAh.g -1 . The results in FIG. 13 show that the capacity retention rate at 5C for 500 cycles is 75.4%.
The layered metal oxides prepared in the above examples were tested for electrochemical properties at different current densities and the test results are shown in tables 1-3.
Table 1 comparison of 100 cycle performance at 0.2C rate for six samples
Table 2 comparison of 200 cycle performance at 1C rate for six samples
Table 3 comparison of 500 cycle performance at 5C rate for six samples
As can be seen from the results of tables 1 to 3, examples 1 to 5 of the present invention were produced by Li + Partially substituted Na 0.766 Ni 0.33 Mn 0.5 Fe 0.1 Ti 0.07 O 2 Ni in (B) 2+ A series of Li with different proportions are synthesized + Substituted Na 0.766+x Li x Ni 0.33- x Mn 0.5 Fe 0.1 Ti 0.07 O 2 (x= 0.02,0.04,0.06,0.08,0.1) positive electrode material. The whole preparation process is simple and efficient in process and low in cost, and the preparation method can be applied to sodium ion batteries, so that the comprehensive performance can be improved, and excellent multiplying power characteristics and cycle stability can be obtained.
Application example 1
A hard carbon matched assembled full cell, button cell model CR2032 was assembled in a glove box filled with an inert atmosphere using Li of example 3 + The substituted sodium ion battery anode material is matched with hard carbon to assemble the full battery.
The assembled full cell was subjected to electrochemical performance testing at a voltage interval of 1.0 to 4.3V (see fig. 14 and 15). Fig. 14 is a charge-discharge curve at 1C for a full cell assembled in example 3 with hard carbon matching. Fig. 15 is a graph of the cycling performance at 1C of a full cell assembled with a hard carbon match for example 3.
The results in fig. 14 show that at 1C (1c=210 mah·g -1 ) The reversible discharge specific capacity of (2) is 183.1_mAh.g -1 . As shown in the results of FIG. 15, the capacity retention rate at 1C for 200 cycles was 80.1%, and the energy density calculated based on the mass of the positive and negative electrode active materials was calculatedAbout 285Wh kg -1 . Therefore, the positive electrode material of the sodium ion battery provided by the embodiment of the invention has the advantages of high ion diffusion rate, excellent rate capability and good application prospect.
In summary, the embodiment of the invention reasonably designs a layered positive electrode oxide to solve the serious high-voltage phase transition of the O3 type positive electrode in the reaction process. As can be seen by comparing the above embodiments, when the lithium substitution amount x exceeds 0.04, the nalmft-0.04 is converted from the P2/O3 complex phase to the pure O3 phase, and the P3 to O3' phase transition in the high voltage region is successfully suppressed. Therefore, all O3 type positive electrode materials (x= 0.06,0.08,0.1) only undergo a simple phase transition of O3-P3 in the voltage range of 2.2-4.3V, and the structural stability is enhanced. Wherein, the O3-NaLNMFT-0.06 has particularly excellent comprehensive performance, and the reversible specific capacity and the working voltage are respectively 138 mAh.g -1 And 3.4V, an energy density of approximately 470 Wh.kg -1 Meanwhile, O3-NaLNMFT-0.06 also shows excellent multiplying power performance and cycle stability, and the 5C multiplying power capacity is up to 119.8 mAh.g -1 The capacity retention rate after 500 circles of circulation reaches 81.6 percent. In addition, the full battery assembled by O3-NaLNMFT-0.06 and the hard carbon negative electrode can still keep 80.1 percent of capacity after being cycled for 200 times at the 1C multiplying power, and has huge industrialization prospect.
In conclusion, by Li + Partially substituted Ni 2+ Can inhibit phase transition from P3 to O3' in O3 type high voltage region, effectively regulate and control phase components, and improve Na + Diffusion rate, comprehensively improves the cycle and multiplying power performance of the material, and has important significance for accelerating the industrialization of sodium ion batteries.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, and alternatives falling within the spirit and principles of the invention.
Claims (10)
1. Li (lithium ion battery) + A substituted sodium ion battery positive electrode material comprising a layered metal oxide having a chemical composition comprising:
Na 0.766+x Li x Ni 0.33-x Mn 0.5 Fe 0.1 Ti 0.07 O 2 wherein 0 is<x≤0.1。
2. Li according to claim 1 + The substituted sodium ion battery positive electrode material is characterized in that the value range of x is 0.04<x≤0.1。
3. Li according to claim 1 + The substituted sodium ion battery positive electrode material is characterized in that the layered metal oxide is a P2/O3 phase oxide or an O3 phase oxide.
4. A Li of claim 1 + The preparation method of the substituted sodium ion battery anode material is characterized by comprising the following steps:
s1, respectively weighing a Li source, a Ni source, a Mn source, a Fe source, a Ti source and a Na source according to a molar ratio x (0.33-x) of 0.5:0.1:0.07 (0.766+x), wherein x is more than 0 and less than or equal to 0.1;
s2, uniformly mixing a Li source, a Ni source, a Fe source, a Mn source, ti and Na sources, transferring into a ball milling tank, adding ethanol as a ball milling medium for ball milling, and drying to obtain precursor powder;
s3, pressing the precursor powder into a sheet shape, and calcining in an air atmosphere to obtain Li + Substituted sodium ion battery positive electrode materials.
5. Li according to claim 4 + The preparation method of the substituted sodium ion battery anode material is characterized in that in S1, the Li source is Li 2 CO 3 The Ni source is NiO, and the Fe source is Fe 2 O 3 The Mn source is MnO 2 The Ti source is TiO 2 The Na source is Na 2 CO 3 。
6. Li according to claim 4 + The preparation method of the substituted sodium ion battery positive electrode material is characterized in that in S2, the addition amount of ethanol is the total mass of precursor powder1 to 5% by weight of the total weight of the composition;
the ball milling conditions are as follows: the rotation speed of the ball milling process is 400r/min, and the time is 4h; the drying temperature was 80 ℃.
7. Li according to claim 4 + The preparation method of the substituted sodium ion battery anode material is characterized in that in S3, the calcination conditions are as follows: the calcination temperature is 900-950 ℃ and the calcination time is 10-15 h.
8. A Li of claim 1 + The application of the substituted sodium ion battery anode material in preparing sodium ion batteries.
9. A sodium ion battery comprising the Li of claim 1 + Substituted sodium ion battery positive electrode materials.
10. The sodium ion battery of claim 9, wherein the sodium ion battery comprises a negative electrode shell, a counter electrode, a separator, a positive electrode sheet, a gasket, a spring sheet, a positive electrode shell, and assembled into a button cell in a glove box filled with an inert atmosphere;
the counter electrode is a sodium sheet prepared from metal sodium; at least one side of the positive electrode sheet comprising Li as set forth in claim 1 + Substituted sodium ion battery positive electrode materials.
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