CN115207340A - Sodium ion battery layered oxide positive electrode material and preparation method and application thereof - Google Patents
Sodium ion battery layered oxide positive electrode material and preparation method and application thereof Download PDFInfo
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- CN115207340A CN115207340A CN202210631638.XA CN202210631638A CN115207340A CN 115207340 A CN115207340 A CN 115207340A CN 202210631638 A CN202210631638 A CN 202210631638A CN 115207340 A CN115207340 A CN 115207340A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 103
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000011734 sodium Substances 0.000 claims abstract description 50
- 239000011572 manganese Substances 0.000 claims abstract description 43
- 239000010406 cathode material Substances 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 19
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000011812 mixed powder Substances 0.000 claims abstract description 8
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 7
- 238000004519 manufacturing process Methods 0.000 claims abstract description 5
- 229910000480 nickel oxide Inorganic materials 0.000 claims abstract description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 3
- 238000007873 sieving Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 150000005324 oxide salts Chemical class 0.000 claims description 2
- 239000001632 sodium acetate Substances 0.000 claims description 2
- 235000017281 sodium acetate Nutrition 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 30
- 238000002441 X-ray diffraction Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 11
- 230000008859 change Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- BNOODXBBXFZASF-UHFFFAOYSA-N [Na].[S] Chemical compound [Na].[S] BNOODXBBXFZASF-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052987 metal hydride Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JOUIQRNQJGXQDC-AXTSPUMRSA-N namn Chemical compound O1[C@@H](COP(O)([O-])=O)[C@H](O)[C@@H](O)[C@@H]1[N+]1=CC=CC(C(O)=O)=C1 JOUIQRNQJGXQDC-AXTSPUMRSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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
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- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a sodium ion battery layered oxide positive electrode material and a preparation method and application thereof. The chemical formula of the layered oxide positive electrode material of the sodium-ion battery is Na 0.67 Mn x Ni y M z O 2 . Manganese oxide, nickel oxide, and an oxide and a sodium salt of M are crushed and mixed according to a stoichiometric ratio; pressing the obtained mixed powder into a sheet or a block; carrying out sectional heat treatment on the flaky or blocky mixed powder; and after the heat treatment is finished, cooling, crushing, grinding and sieving the sample to obtain the layered oxide cathode material of the sodium-ion battery. The sodium ion battery anode material prepared by the invention has high purity and high valence stateThe Ni element activates the activity in the material and has the characteristics of high multiplying power, long service life and high specific capacity. The invention has simple process and low requirement on equipment, can be matched with the existing production line of the lithium ion battery, and is favorable for marketization popularization.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery manufacturing, and particularly relates to a layered oxide positive electrode material of a sodium ion battery, and a preparation method and application thereof.
Background
In the large context of the "dual carbon" strategic goal, the development of clean energy is an essential part thereof. Wind energy and solar energy are used as clean energy for the key development of China, and have gradually overtaken the traditional hydroelectric power generation in recent years. However, due to environmental constraints, wind energy and solar energy have intermittent and fluctuating characteristics, and direct integration into the power grid causes impact on the power grid system. Therefore, a storage end is required to be added between the power generation end and the power grid to serve as a buffer for new energy utilization, and a power generation-energy storage-power grid-user intelligent power grid structure is formed.
The traditional electrochemical energy storage equipment comprises a lithium ion battery, a nickel-metal hydride battery, a lead-acid battery, a super capacitor, a sodium-sulfur battery and the like, wherein the performance of the lithium ion battery and the performance of the sodium-sulfur battery can both reach 120Wh/kg, and the performance requirement of large-scale energy storage can be met. However, lithium ion batteries are limited by lithium resources, and sodium-sulfur batteries are difficult to be practically used because they must be operated in a high-temperature environment. The sodium element and the lithium element belong to the same group of elements and have similar physical and chemical properties, and the sodium element is the sixth most abundant element in the earth crust, accounts for about 2.4 percent, and has extremely abundant reserves. In addition, the sodium ion battery has a similar working principle as the lithium ion battery, and the energy density can reach a similar level as the lithium ion battery. Sodium ion batteries are one of the best choices as large-scale energy storage devices, combining cost and performance considerations.
As one of the important components of a sodium ion battery, various positive electrode materials are widely studied. Wherein the theoretical specific capacity of the P2 type layered oxide anode material can reach 175mAh g -1 The structure is stable, sodium ions are transmitted in the structure through a channel connected with the surface, and the material has a fast sodium ion transmission rate and is one of the most promising materials. However, the application of the material depends onHowever, there are some problems: 1) Phase change easily occurs in the circulation process, and a stable P-type structure is damaged; 2) In the process of sodium ion insertion and extraction, the volume of the material can change, and the structure is damaged by large volume change; 3) After the material is charged to a high voltage, a voltage hysteresis phenomenon is shown in the discharging process, and energy loss is brought; 4) On the premise of stable circulation, the specific capacity of the material is not high. These problems have restricted the practical application of the material.
The patent sodium-ion battery manganese-based positive electrode material (publication number: CN 107403915A) describes the preparation method of manganese-based positive electrode material and the component NaMn of the material X Ti Y M 1-X-Y O 2 Where M = Ni, co or Fe. Similar materials leave less capacity for stable circulation after abandoning the capacity in the unstable high voltage interval and the capacity in the low voltage interval which is difficult to utilize, and are difficult to meet the actual requirement. Aiming at the problem, the invention develops artificial Ni production in different systems 3+ Method for synthesizing ionic material and using Ni 3+ The ions perform capacity enhancement on different materials. Preparing a layered oxide anode material Na of a sodium-ion battery by utilizing a solid-phase reaction 0.67 Mn x Ni y M z O 2 (x + y + z = 1), the material has extremely small volume change in the circulation process, and has the characteristics of long circulation and high multiplying power.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a sodium-ion battery layered oxide positive electrode material with low strain, high capacity, stable circulation and excellent rate performance, and a preparation method and application thereof.
The purpose of the invention is realized by the following technical scheme:
a P2 type sodium ion battery layered oxide anode material with a chemical formula of Na a Mn x Ni y M z O 2 (ii) a Wherein a is 0.6-0.8; x + y + z =1, x is 0.35-0.67, y is 0.17-0.38, z is 0.16-0.33; m is at least one of Co, fe, cu, al, mg and Ti, the average valence of M is b, and the chemical formula satisfies
The P2 type sodium ion battery layered oxide positive electrode material satisfying the chemical formula provided by the invention is prepared by introducing Ni 3+ The ions eliminate the cyclic strain and improve the specific capacity at the same time.
Preferably, the sodium-ion battery layered oxide cathode material is single crystal particles with the size of 1-5 μm.
The preparation method of the layered oxide cathode material of the sodium-ion battery comprises the following steps:
(1) Crushing and mixing manganese oxide, nickel oxide, and oxide and sodium salt of M according to a stoichiometric ratio;
(2) Pressing the mixed powder obtained in the step (1) into a sheet or a block;
(3) Carrying out sectional heat treatment on the flaky or blocky mixed powder in the step (2);
(4) And (4) after the heat treatment in the step (3) is finished, cooling, crushing, grinding and sieving the sample to obtain the sodium ion battery layered oxide positive electrode material.
Preferably, the crushing in the step (1) is a ball milling process, the ball mill is a pendulum vibration ball mill or a planetary ball mill, the ball-material ratio is 1.
Preferably, the sodium salt is present in step (1) in an excess of 5 to 15% (relative to the stoichiometric ratio).
Preferably, the sodium salt in step (1) is at least one of sodium carbonate, sodium hydroxide and sodium acetate.
Preferably, the pressure for pressing in the step (2) is 5-20MPa.
Preferably, the atmosphere of the heat treatment in the step (3) is air or oxygen.
Preferably, the step (3) of the staged heat treatment is that the calcining temperature of the first stage is 400-600 ℃, and the calcining time is 4-8 h; the second stage calcining temperature is 800-1000 ℃, and the calcining time is 8-16 h; the calcining temperature of the third stage is 600-800 ℃, and the calcining time is 8-16 h.
Preferably, the cooling method in the step (4) is one of air cooling, water cooling and liquid nitrogen cooling.
The layered oxide cathode material of the sodium-ion battery is applied to the preparation of the sodium-ion battery.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) In the invention, the valence state of Ni in the material is improved by utilizing the calcination process of the sectional heat treatment, so that sodium ions are distributed more uniformly in the material, obvious phase change is inhibited, and the volume change in the circulation process is reduced to be less than 1 percent.
(2) Na produced in the present invention 0.67 Mn x Ni y M z O 2 (x + y + z = 1) the activity of the material is improved by using higher-valence Ni element, and the reversible capacity is improved to 110mAh g in the voltage range of 2.0-4.25V -1 As described above.
(3) Na produced in the present invention 0.67 Mn x Ni y M z O 2 (x + y + z = 1) cycles in the voltage range of 2.0-4.25V, and there is almost no voltage hysteresis.
(4) Na produced in the invention 0.67 Mn x Ni y M z O 2 (x + y + z = 1) benefits from a stable structure and rapid sodium ion transport at 1 ag -1 Capacity retention rate after 2000 cycles at high current density of 60%.
Drawings
Fig. 1 is an SEM image of a layered oxide positive electrode material of a sodium ion battery prepared in example 1;
fig. 2 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in example 1;
FIG. 3 shows the layered oxide positive electrode material of the Na-ion battery prepared in example 1 at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
FIG. 4 shows the layered oxide positive electrode material of the sodium-ion battery prepared in example 1 at 1 Ag -1 Under currentA long cycle performance map;
FIG. 5 layered oxide cathode Material of sodium ion Battery prepared in example 1 assembled into full Battery at 1 ag -1 Long cycle performance plot under current;
figure 6 in-situ XRD patterns and changes in volume during cycling of the layered oxide positive electrode material of the sodium-ion battery prepared in example 1;
fig. 7 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in example 2;
FIG. 8 shows the layered oxide positive electrode material of the sodium-ion battery prepared in example 2 at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
fig. 9 is an in-situ XRD pattern and volume change thereof during the cycle of the layered oxide positive electrode material of the sodium-ion battery prepared in example 2;
fig. 10 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in comparative example 1;
FIG. 11 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 1 is 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
fig. 12 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in comparative example 2;
FIG. 13 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 2 is 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
fig. 14 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in comparative example 3;
FIG. 15 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 3 is 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
FIG. 16 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 3 is 50mA g -1 A cycle performance diagram of a voltage range of 2.0-4.25V under current;
FIG. 17 shows the layered oxide positive electrode material of the sodium-ion battery prepared in example 3 at 50mA g -1 Charging at a current in the voltage range of 2.0-4.0VA discharge curve graph;
FIG. 18 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 4 is at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.0V under current;
FIG. 19 shows the layered oxide positive electrode material of the Na-ion battery prepared in example 4 at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.1V under current;
FIG. 20 shows that the layered oxide positive electrode material of the Na-ion battery prepared in comparative example 5 is at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.1V under current;
fig. 21 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in example 5;
FIG. 22 shows the layered oxide positive electrode material of the sodium-ion battery prepared in example 5 at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
fig. 23 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in example 6;
FIG. 24 shows the layered oxide positive electrode material of the Na-ion battery prepared in example 6 at 50mA g -1 A charge-discharge curve diagram of a voltage range of 2.0-4.25V under current;
fig. 25 is an XRD pattern of the layered oxide positive electrode material of the sodium-ion battery prepared in example 7;
FIG. 26 shows the layered oxide positive electrode material of the Na-ion battery prepared in example 7 at 50mA g -1 A charge-discharge curve chart of a voltage range of 2.0-4.3V under current.
Detailed Description
The present invention will be further described with reference to specific examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1
The molecular formula of the preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment is Na 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 ，
The sodium source is Na 2 CO 3 The method comprises the following steps:
manganese oxide, nickel oxide, cobalt oxide and sodium carbonate powder were weighed in stoichiometric proportions with a 10% sodium carbonate excess. All powders were mixed using a planetary ball mill with a ball to feed ratio of 1:20, the rotating speed is 300 r/min, and the ball milling time is 8 hours. The obtained mixed powder is pressed into a square block with the side length of 3 cm and the thickness of 1 cm by a tablet press under 10MPa, and the square block is placed in a porcelain boat and transferred into a muffle furnace for calcination. In the first stage, the temperature is increased to 500 ℃ at the speed of 5 ℃/min, the temperature is kept for 5h, the temperature is increased to 850 ℃ at the speed of 5 ℃/min, the temperature is reduced to 700 ℃ after the temperature is kept for 12h, a sample is obtained by air cooling after the temperature is kept for 12h, and the sample is ground and sieved to obtain the Na-ion battery anode material 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 。
The SEM image of the layered oxide cathode material of the sodium-ion battery prepared in this example is shown in fig. 1.
The XRD pattern of the layered oxide cathode material of sodium-ion battery prepared in this example is shown in fig. 2.
Na prepared in this example 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 The positive electrode material of the sodium-ion battery is used for the sodium-ion battery: adding Na as a positive electrode material 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 Uniformly mixing a conductive agent (Super-P) and a binder (PVDF) according to the mass ratio of 8; in an argon atmosphere glove box, metal sodium is used as a counter electrode, and electrolyte is 1M NaClO 6 Dissolved in EC and PC, 5% fec as additive, assembled into button cells for testing. The test conditions were that the charge and discharge magnification was 50mA g -1 The test shows that the cut-off voltage of charging and discharging is 2-4.25V (vs. Na) + /Na)。50mA g -1 The charge and discharge curves obtained by the test are shown in figure 3. As can be seen from the graph, the first discharge capacity reached 110mAh g -1 And the discharge curve and the charge curve are basically superposed, and the voltage hysteresis phenomenon hardly exists. With 1A g -1 The cycle performance obtained from the high current test is shown in fig. 4. From the figure canIt is known that the capacity retention rate after 1000 cycles was 80%, and 62% after 2000 cycles.
Na prepared in this example 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 The positive electrode material of the sodium-ion battery and the hard carbon material are paired to assemble the whole battery, and the long-cycle performance is shown in figure 5. As can be seen from the figure, the full cell can be cycled for 2000 cycles, with a capacity retention of 66%.
Na prepared in this example 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 The in-situ XRD pattern of the sodium-ion battery cathode material during the circulation process is shown in figure 6, and the volume change is 0.6%.
Example 2
The preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment has a molecular formula of Na 0.67 Mn 0.40 Ni 0.27 Co 0.33 O 2 ，
The sodium source is Na 2 CO 3 The method comprises the following steps:
manganese oxide, nickel oxide, cobalt oxide and sodium carbonate powder were weighed in stoichiometric proportions, with a 10% sodium carbonate excess. All powders were mixed using a planetary ball mill, the ball to feed ratio being 1:20, the rotating speed is 300 r/min, and the ball milling time is 8 hours. The obtained mixed powder is pressed into a square block with the side length of 3 cm and the thickness of 1 cm by a tablet press under the pressure of 10MPa, and the square block is placed in a porcelain boat and transferred into a tubular furnace for calcination under the atmosphere of oxygen. In the first stage, the temperature is raised to 500 ℃ at the speed of 5 ℃/min, the temperature is kept for 5h, the temperature is raised to 900 ℃ at the speed of 5 ℃/min, the temperature is reduced to 700 ℃ after the temperature is kept for 12h, a sample is obtained by water cooling after the temperature is kept for 12h, and the sample is ground and sieved to obtain the Na anode material of the sodium-ion battery 0.67 Mn 0.40 Ni 0.27 Co 0.33 O 2 。
The XRD pattern of the positive electrode material for sodium-ion battery prepared in this example is shown in fig. 7. The phases were pure as in example 1.
Na prepared in this example 0.67 Mn 0.40 Ni 0.27 Co 0.33 O 2 The positive electrode material for sodium ion battery was used for sodium ion battery in the same manner as in example 1. The test results show that Na prepared in this example 0.67 Mn 0.40 Ni 0.27 Co 0.33 O 2 The charge-discharge curve of the layered oxide positive electrode material of the sodium-ion battery is shown in fig. 8. The first discharge capacity is improved compared with that of the embodiment 1 and reaches 130mAh g -1 。
The in-situ XRD pattern of the sodium-ion battery positive electrode material prepared in this example during cycling is shown in fig. 9, with a volume change of 0.7%. In combination with example 1, the layered oxide positive electrode material for a sodium-ion battery satisfying the chemical formula has a characteristic of low strain.
Comparative example 1
Layered oxide cathode material of sodium-ion battery prepared in comparative example 1, raw material components of layered oxide cathode material and Na prepared in example 1 0.67 Mn 0.45 Ni 0.22 Co 0.33 O 2 And (3) uniformly, but in a difference, a section of calcination process is adopted, and the precursor is calcined at 850 ℃ for 15h and quenched to obtain a sample.
The XRD pattern of the positive electrode material for sodium-ion battery prepared in this comparative example is shown in fig. 10. Ni in the material will be generated due to one-stage high-temperature calcination 3+ Reduction to Ni 2+ The Ni element is difficult to completely enter into crystal lattices, and NiO mixed phase appears in the material.
The charge and discharge curves of the positive electrode material for the sodium-ion battery prepared in this comparative example are shown in fig. 11. Due to the existence of NiO mixed phase, active elements in the material are reduced, and the specific charge capacity of the first circle is 83mAh g -1 The first circle discharge specific capacity is 100mAh g -1 The specific charge-discharge capacity is lower than that of example 1, which illustrates the necessity of a multistage calcination process.
Comparative example 2
Comparative example 2 preparation of layered oxide cathode Material Na for sodium ion Battery 0.67 Mn 0.50 Ni 0.17 Co 0.33 O 2 ，
The preparation was in accordance with example 1.
Layered oxide cathode material Na for bulk sodium-ion battery obtained in comparative example 2 0.67 Mn 0.50 Ni 0.17 Co 0.33 O 2 The XRD pattern of (A) is shown in FIG. 12.
Na obtained in comparative example 2 0.67 Mn 0.50 Ni 0.17 Co 0.33 O 2 For sodium ion batteries: the measurement was carried out in the same manner as in example 1. FIG. 13 shows Na obtained in comparative example 2 0.67 Mn 0.50 Ni 0.17 Co 0.33 O 2 The first charge-discharge curve of the anode material shows that the first discharge capacity is less than 90mAh g -1 . Compared with the embodiment 1 and the embodiment 2, the activity of the material is obviously improved by oxidizing the Ni element into a higher valence state, and the specific capacity is obviously improved in the range of 2-4.25V.
Comparative example 3
Comparative example 3 preparation of layered oxide cathode Material Na for sodium ion Battery 0.67 Mn 0.35 Ni 0.32 Co 0.33 O 2 ，
The preparation was in accordance with example 1.
Layered oxide cathode material Na for bulk sodium-ion battery obtained in comparative example 3 0.67 Mn 0.35 Ni 0.32 Co 0.33 O 2 As shown in fig. 14, a large amount of NiO impurity phase was observed under the chemical formula boundary conditions.
Na obtained in comparative example 3 0.67 Mn 0.35 Ni 0.32 Co 0.33 O 2 For sodium ion batteries: the measurement was performed in the same manner as in example 1. FIG. 15 shows Na obtained in comparative example 3 0.67 Mn 0.35 Ni 0.32 Co 0.33 O 2 The first charge-discharge curve of the positive electrode material shows that the first discharge capacity is 110mAh g -1 Left and right. In comparison with example 2, it can be seen that, beyond the formula boundary conditions, ni 3+ The increase in ions also does not increase the capacity.
Na obtained in comparative example 3 0.67 Mn 0.35 Ni 0.32 Co 0.33 O 2 For sodium dissociationThe sub-battery is at 50mA g -1 The current density lower cycle chart is shown in FIG. 16, and the specific capacity is lower than 100mAh g after 100 cycles -1 。
Example 3
The molecular formula of the preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment is Na 0.67 Mn 0.62 Ni 0.38 O 2 ，
The preparation was in accordance with example 1.
Na prepared in this example 0.67 Mn 0.62 Ni 0.38 O 2 The positive electrode material of the sodium ion battery is used for the sodium ion battery, the measurement mode is the same as that of the embodiment 1, and the test voltage range is different and is 2.0-4.0V. The charging and discharging curves of the first turn and the second turn are shown in figure 17.
Comparative example 4
The preparation method of the layered oxide positive electrode material of the sodium-ion battery of the comparative example has the molecular formula of Na 0.67 Mn 0.67 Ni 0.33 O 2 ，
The preparation was in accordance with example 1.
Na prepared in this comparative example 0.67 Mn 0.67 Ni 0.33 O 2 The positive electrode material for sodium ion battery was used for sodium ion battery, and the measurement was carried out in the same manner as in example 3. The charging and discharging curves of the first circle and the second circle are shown in figure 18, and the comparison example 3 can find that the specific capacity can be effectively improved in the system by improving the valence state of the Ni element.
Example 4
The preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment has a molecular formula of Na 0.67 Mn 0.45 Ni 0.22 Fe 0.33 O 2 ，
The preparation was in accordance with example 1.
Na prepared in this example 0.67 Mn 0.45 Ni 0.22 Fe 0.33 O 2 The positive electrode material of the sodium-ion battery is used for the sodium-ion battery, the measurement mode is the same as that of the embodiment 1, and the test voltage range is different and is 2.0-4.1V. The charging and discharging curves of the first circle and the second circle are shown in figure 19.
Comparative example 5
The preparation method of the layered oxide positive electrode material of the sodium-ion battery of the comparative example has the molecular formula of Na 0.67 Mn 0.50 Ni 0.17 Fe 0.33 O 2 ，
The preparation was in accordance with example 1.
Na prepared in this comparative example 0.67 Mn 0.50 Ni 0.17 Fe 0.33 O 2 The positive electrode material for sodium ion battery was used for sodium ion battery, and measured in the same manner as in example 4. The charging and discharging curves of the first circle and the second circle are shown in fig. 20, and the comparison example 4 shows that the specific capacity can be effectively improved by improving the valence state of the Ni element in the system.
Example 5
The molecular formula of the preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment is Na 0.67 Mn 0.53 Ni 0.3 Al 0.05 Fe 0.12 O 2 ，
The preparation was in accordance with example 1, with an XRD as shown in figure 21.
Na prepared in this example 0.67 Mn 0.53 Ni 0.3 Al 0.05 Fe 0.12 O 2 The positive electrode material of the sodium-ion battery is used for the sodium-ion battery, the measurement mode is the same as that of the example 1, and the charging and discharging curve of the first ten circles is shown in fig. 22.
Example 6
The preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment has a molecular formula of Na 0.67 Mn 0.53 Ni 0.3 Cu 0.085 Ti 0.085 O 2 ，
The preparation was in accordance with example 1, with XRD as shown in figure 23.
Na prepared in this example 0.67 Mn 0.53 Ni 0.3 Cu 0.085 Ti 0.085 O 2 The positive electrode material of the sodium-ion battery is used for the sodium-ion battery, the measurement mode is the same as that of the example 1, and the charging and discharging curve of the first ten circles is shown in fig. 24.
Example 7
The molecular formula of the preparation method of the layered oxide cathode material of the sodium-ion battery of the embodiment is Na 0.67 Mn 0.53 Ni 0.3 Mg 0.085 Ti 0.085 O 2 ，
The preparation was in accordance with example 1, with an XRD as shown in figure 25.
Na prepared in this example 0.67 Mn 0.53 Ni 0.3 Mg 0.085 Ti 0.085 O 2 The positive electrode material of the sodium-ion battery is used for the sodium-ion battery, the measurement mode is the same as that of the embodiment 1, the voltage interval is changed to be 2.0-4.3V, and the charging and discharging curves of the first ten circles are shown in figure 26.
The present invention is not limited to the above embodiments, and various other modifications, substitutions or alterations can be made without departing from the basic technical idea of the invention by using the common technical knowledge and the conventional means in the field according to the above content of the present invention, and the present invention falls within the protection scope of the claims of the present invention.
Claims (10)
1. The layered oxide cathode material of the sodium-ion battery is characterized in that the chemical formula is Na a Mn x Ni y M z O 2 (ii) a Wherein a is 0.6-0.8; x + y + z =1, x is 0.35-0.67, y is 0.17-0.38, z is 0.16-0.33; m is at least one of Co, fe, cu, al, mg and Ti,the average valence of M is b, and the chemical formula satisfies
2. The preparation method of the layered oxide cathode material of the sodium-ion battery, which is described in claim 1, is characterized by comprising the following steps:
(1) Crushing and mixing manganese oxide, nickel oxide, and M oxide and sodium salt according to a stoichiometric ratio;
(2) Pressing the mixed powder obtained in the step (1) into a sheet or a block;
(3) Carrying out sectional heat treatment on the flaky or blocky mixed powder in the step (2);
(4) And (4) after the heat treatment in the step (3) is finished, cooling, crushing, grinding and sieving the sample to obtain the sodium ion battery layered oxide positive electrode material.
3. The preparation method according to claim 2, wherein the crushing in the step (1) is a ball milling process, the ball mill is a pendulum vibration ball mill or a planetary ball mill, the ball-material ratio is 1.
4. The process according to claim 2, wherein the sodium salt is in excess of 5 to 15% in step (1).
5. The method according to claim 2, wherein the sodium salt in step (1) is at least one of sodium carbonate, sodium hydroxide and sodium acetate.
6. The production method according to claim 2, wherein the pressure of the pressing in the step (2) is 5 to 20MPa.
7. The method according to claim 2, wherein an atmosphere of the heat treatment in the step (3) is air or oxygen.
8. The preparation method according to claim 2, wherein the staged heat treatment in step (3) is carried out at a calcination temperature of 400-600 ℃ for 4-8 h in the first stage; the second stage calcining temperature is 800-1000 ℃, and the calcining time is 8-16 h; the calcining temperature of the third stage is 600-800 ℃, and the calcining time is 8-16 h.
9. The method of claim 2, wherein the cooling in step (4) is one of air cooling, water cooling and liquid nitrogen cooling.
10. The use of the layered oxide positive electrode material of a sodium-ion battery of claim 1 in the manufacture of a sodium-ion battery.
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| CN115448385A (en) * | 2022-11-10 | 2022-12-09 | 山东昭文新能源科技有限公司 | Four-phase mixed sodium-ion battery layered oxide positive electrode material and preparation method thereof |
| CN115924978A (en) * | 2022-11-23 | 2023-04-07 | 湖北万润新能源科技股份有限公司 | Manganese-based layered sodium-ion battery positive electrode material and preparation method and application thereof |
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| CN115810743A (en) * | 2022-12-14 | 2023-03-17 | 南京大学 | Single crystal layered oxide positive electrode material, preparation method and application in sodium ion battery |
| CN115810743B (en) * | 2022-12-14 | 2023-08-04 | 南京大学 | Single crystal layered oxide positive electrode material, preparation method and application thereof in sodium ion battery |
| CN117117174A (en) * | 2023-10-25 | 2023-11-24 | 宁波容百新能源科技股份有限公司 | Sodium ion battery positive electrode material, and preparation method and application thereof |
| CN117117174B (en) * | 2023-10-25 | 2024-03-19 | 宁波容百新能源科技股份有限公司 | Sodium ion battery positive electrode material, and preparation method and application thereof |
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