CN117855465A - Cation modified high-energy-density lithium nickel manganese oxide spinel positive electrode material and preparation method and application thereof - Google Patents
Cation modified high-energy-density lithium nickel manganese oxide spinel positive electrode material and preparation method and application thereof Download PDFInfo
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 75
- 239000011029 spinel Substances 0.000 title claims abstract description 75
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 49
- 150000001768 cations Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000463 material Substances 0.000 claims abstract description 31
- 238000000498 ball milling Methods 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 47
- 238000001354 calcination Methods 0.000 claims description 39
- 238000001816 cooling Methods 0.000 claims description 36
- 238000010438 heat treatment Methods 0.000 claims description 36
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical group O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 28
- 239000002243 precursor Substances 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 21
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011572 manganese Substances 0.000 claims description 18
- 238000000227 grinding Methods 0.000 claims description 16
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 14
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 14
- 229910052748 manganese Inorganic materials 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000002612 dispersion medium Substances 0.000 claims description 11
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims description 10
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 10
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical group [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 9
- -1 cation modified lithium nickel manganese oxide Chemical class 0.000 claims description 7
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 claims description 6
- 229910001195 gallium oxide Inorganic materials 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 229910013716 LiNi Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229940093474 manganese carbonate Drugs 0.000 claims description 3
- 235000006748 manganese carbonate Nutrition 0.000 claims description 3
- 239000011656 manganese carbonate Substances 0.000 claims description 3
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims description 3
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 3
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000005245 sintering Methods 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 13
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 9
- 239000010406 cathode material Substances 0.000 description 9
- 239000012071 phase Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 102100028292 Aladin Human genes 0.000 description 2
- 101710065039 Aladin Proteins 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000012982 microporous membrane Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 description 1
- 229910015902 Bi 2 O 3 Inorganic materials 0.000 description 1
- 206010021143 Hypoxia Diseases 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 241000218378 Magnolia Species 0.000 description 1
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the field of lithium ion batteries, and discloses a cation doping modified high-energy density spinel lithium nickel manganese oxide positive electrode material and a preparation method thereof. The spinel lithium nickel manganese oxide positive electrode material with high energy density can widen a voltage window to below 3V and even reach 1.5V, and can show higher specific discharge capacity. Through element doping, the stability of the material can be effectively improved, and the multiplying power performance of the material is improved, so that the spinel lithium nickel manganese oxide anode material with high energy density is obtained. The preparation method provided by the invention is a ball milling combined high-temperature sintering synthesis method, has simple process, is convenient to operate, has low cost, and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a cation modified high-energy density lithium nickel manganese oxide spinel positive electrode material, and a preparation method and application thereof.
Background
Since lithium ion batteries are commercialized for the first time, the lithium ion batteries have been widely applied to various fields of portable devices, electric automobiles and the like, and the life style of the lithium ion batteries is thoroughly changed.
Spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) is the only high voltage in all commercial positive electrode materials>4.5V) positive electrode. However, the theoretical energy density (> 600 Wh/kg) is still less than that of the high nickel layered oxide [ ]>800 Wh/kg) and lithium-rich layered oxide>900 Wh/kg). One of the strategies to increase the spinel LNMO energy density is to broaden the cut-off voltage from 3V to below 3V to increase the capacity, thereby achieving an increase in energy density. In addition to that, with LiCoO 2 And Li (Ni) 1/3 Co 1/3 Mn 1/3 )O 2 The representative layered positive electrode is lower in cost. Therefore, LNMO is considered as a very promising high energy density cathode material.
However, spinel-type lithium nickel manganese oxide materials have disadvantages such as a low capacity retention rate, further improvement in cycle performance and rate performance, and the like. There is therefore still a need for more intensive research into materials, for improved preparation processes and for improved properties.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the primary purpose of the invention is to provide a cation modified high-energy-density lithium nickel manganese oxide spinel anode material; the inventor finds that the discharge specific capacity of the lithium nickel manganese oxide material can be greatly improved by reducing the cut-off voltage to 1.5V through researches; the length of the lithium nickel manganese oxide material-2.7 platforms can be restrained through element doping, so that the comprehensive electrochemical performance of the material is improved, and the lithium nickel manganese oxide spinel anode material with high energy density is realized.
The invention also aims to provide a preparation method of the cation modified high-energy-density lithium nickel manganese oxide spinel positive electrode material.
It is still another object of the present invention to provide the use of the above-described cationically modified high energy density lithium nickel manganese oxide spinel cathode material.
The aim of the invention is achieved by the following technical scheme:
a positive electrode material of cation modified high-energy density lithium nickel manganese oxide spinel has the following chemical general formula:
LiNi 0.5 Mn 1.5-x M x O 4 wherein M is Fe, co and/or Ga,0<x<0.5。
The nickel lithium manganate spinel positive electrode material reduces the cutoff voltage to 1.5V, and improves the specific discharge capacity, thereby realizing high energy density of more than 900 Wh/kg.
The preparation method of the cation modified high-energy-density lithium nickel manganese oxide spinel anode material comprises the following operation steps:
(1) Mixing a lithium source, a nickel source, a manganese source and an M source by adopting wet ball milling to obtain a mixed precursor;
(2) Heating the mixed precursor obtained in the step (1) to 1000 ℃ at a heating rate of 1-10 ℃/min for first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 1-10 ℃/min, grinding, heating to 700 ℃ at a heating rate of 1-10 ℃/min for second calcination, wherein the calcination time is 24 hours, then cooling to room temperature at a cooling rate of 1-10 ℃/min, and grinding the obtained calcination product to obtain the cation modified lithium nickel manganese oxide spinel positive electrode material with high energy density.
In the step (1), the lithium source is lithium carbonate, lithium hydroxide or lithium oxide, the nickel source is nickel oxide or nickel carbonate, and the manganese source is manganese dioxide or manganese carbonate; the M source is at least one of ferroferric oxide, cobaltosic oxide and gallium oxide.
More preferably, in the step (1), the lithium source is lithium carbonate, the nickel source is nickel protoxide, the manganese source is manganese dioxide, and the M source is at least one of ferroferric oxide, cobaltosic oxide and gallium oxide.
In the step (1), the molar ratio of the lithium source calculated as lithium element, the nickel source calculated as nickel element, the manganese source calculated as manganese element and the M source calculated as M element is (1.03-1.08): 0.5: y: x is preferably 1.05:0.5: y: x, wherein 0< x <0.5, y=1.5-x.
And (3) adopting absolute ethyl alcohol or deionized water as a dispersion medium for the wet ball milling and mixing in the step (1).
The ball weight ratio of the wet ball milling mixed materials adopted in the step (1) is 5:1-8:1, the ball milling rotating speed is 300-500 rpm, and the ball milling time is 6-10 hours.
The cation modified high-energy-density lithium nickel manganese oxide spinel anode material is applied to power lithium batteries and consumer electronics lithium ion batteries.
Compared with the prior lithium ion battery technology, the cation modified high-energy density lithium nickel manganese oxide spinel positive electrode material and the preparation method thereof have the following advantages and effects:
(1) The positive electrode material of the cation modified high-energy density lithium nickel manganese oxide spinel provided by the invention widens the cut-off voltage from 3V to below 3V (1.5V) and realizes higher specific discharge capacity.
(2) The cation modified high-energy density lithium nickel manganese oxide spinel positive electrode material provided by the invention is doped with proper M cations, so that the stability of the material can be effectively improved, the cycle life of the material can be prolonged, and the rate performance of the material can be improved.
(3) The cation modified high-energy-density lithium nickel manganese oxide spinel positive electrode material provided by the invention is doped with proper M cations, so that the cut-off voltage is reduced to below 3V (1.5V), and the energy density can be improved and the cycle stability can be improved.
(4) The positive electrode material of the cation modified high-energy-density lithium nickel manganese oxide spinel provided by the invention has a pure-phase spinel structure, and has the advantages of high product purity, no impurity phase and good product consistency.
(5) The preparation method of the cation modified high-energy-density lithium nickel manganese oxide spinel anode material provided by the invention is a high-temperature solid phase synthesis method, and compared with wet chemical synthesis methods such as a coprecipitation method, a sol-gel method, a hydrothermal method and the like, the preparation method is simple in process, convenient to operate, low in cost and more beneficial to industrial production.
Drawings
FIG. 1 is a scanning electron microscope image of a lithium nickel manganese oxide spinel positive electrode material obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of the lithium nickel manganese oxide spinel positive electrode material obtained in example 2 of the present invention;
FIG. 3 is an XRD pattern of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 2 of the present invention;
FIG. 4 is a graph showing the cycle performance of the lithium nickel manganese oxide spinel positive electrode materials obtained in examples 1-4 of the present invention at 0.5C (1C=200 mAh/g);
FIG. 5 is a graph showing the charge and discharge curves of the lithium nickel manganese oxide spinel positive electrode materials obtained in examples 1 and 2 of the present invention at 0.2C;
FIG. 6 is a graph showing the rate performance of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 2 of the present invention at 0.2C, 0.5C, 1C, 2C, and 0.2C for each cycle of 5 cycles;
FIG. 7 is a graph showing energy density comparisons of the lithium nickel manganese oxide spinel positive electrode materials obtained in examples 1 and 2 of the present invention at 0.2C, 0.5C, 1C, 2C, and 0.2C for each cycle of 5 cycles;
FIG. 8 is a graph showing the cycle performance of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 5 of the present invention at 0.2C;
FIG. 9 is a graph showing the charge and discharge curves of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 5 of the present invention at 0.2C;
FIG. 10 is a graph showing the cycle performance at 0.2C of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 6 of the present invention;
fig. 11 is a charge-discharge curve of the lithium nickel manganese oxide spinel positive electrode material obtained in examples 1 and 6 of the present invention at 0.2C.
Detailed Description
The present invention is further illustrated below in conjunction with specific examples, but should not be construed as limiting the invention. The technical means used in the examples are conventional means well known to those skilled in the art unless otherwise indicated. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
As previously described, the first aspect of the present invention provides a cation modified high energy density lithium nickel manganese oxide spinel positive electrode material having the chemical formula LiNi 0.5 Mn 1.5-x M x O 4 (M is Fe, coAnd/or Ga,0<x<0.5)。
As previously described, a second aspect of the present invention provides a process for preparing the modified spinel lithium nickel manganese oxide of the first aspect, the process comprising the steps of:
(1) Mixing a lithium source, a nickel source, a manganese source and an M source by adopting wet ball milling to obtain a mixed precursor;
(2) And (3) heating the mixed precursor obtained in the step (1) to 700-1000 ℃ at a heating rate of 1-10 ℃/min for calcination, wherein the calcination time is 12-24 hours, and then cooling to room temperature at a cooling rate of 1-10 ℃/min to obtain the cation modified lithium nickel manganese oxide spinel positive electrode material with high energy density, wherein the chemical general formula of the cation modified lithium nickel manganese oxide spinel positive electrode material is (M is Fe, co and/or Ga, and x is 0< 0.5).
In the present invention, in the step (1), the lithium source may be lithium carbonate, lithium hydroxide, or lithium oxide, the nickel source may be nickel oxide, or nickel carbonate, and the manganese source may be manganese dioxide, or manganese carbonate.
Preferably, in step (1), the lithium source is lithium carbonate, the nickel source is nickel oxide, the manganese source is manganese dioxide, and the M source is at least one of ferroferric oxide, cobaltosic oxide, and gallium oxide.
Preferably, in the step (1), the lithium source as lithium element, the nickel source as nickel element, the manganese source as manganese element and the M source as M element are used in a molar ratio of (1.03-1.08): 0.5: y: x is preferably 1.05:0.5: y: x, wherein 0< x <0.5, y=1.5-x.
In a preferred case, the amount of the lithium source added in terms of lithium element is 1.03 to 1.08 times the target amount. The inventor finds that under the condition of the addition amount, the volatilization loss of the lithium source in the high-temperature calcination process can be supplemented, and properly increasing the content of lithium can effectively improve the stability of the material and prolong the cycle life of the material, so that the addition amount is generally controlled to be 1.03-1.08 times of the target amount.
In the present invention, the amount of the M source to be incorporated into the M element is controlled so that the obtained LiNi 0.5 Mn 1.5 O 4 -M x X in the middle<0.5. The inventor finds that the doping is too little, and the modification effect on the lithium nickel manganese oxide is not obvious; too much incorporation, while improving stability, can affect capacity.
Preferably, the conditions of the wet ball milling mixture in step (1) at least satisfy: the dispersion medium is absolute ethyl alcohol or deionized water.
In the present invention, the addition amount of the dispersion medium is not particularly limited, and for example, the addition amount of the dispersion medium is 20 to 40mL for a ball mill pot having a volume of 80 mL.
Preferably, the conditions of the wet ball milling mixture at least satisfy the following conditions: the weight ratio of the ball materials is 5:1-8:1, the weight ratio of the ball materials represents the weight ratio of agate balls to raw materials, the ball milling rotating speed is 400-600 rpm, and the ball milling time is 6-10 hours. The inventor finds that the powder can be more fully mixed and crushed under the condition that the weight ratio of the ball materials is controlled to be 5:1-8:1, and the ineffective loss of energy sources is avoided.
Preferably, in the step (2), the mixed precursor obtained in the step (1) is heated to 1000 ℃ at a heating rate of 1-10 ℃/min for first calcination, the calcination time is 12 hours, then cooled to room temperature at a cooling rate of 1-10 ℃/min, ground and then heated to 700 ℃ at a heating rate of 1-10 ℃/min for second calcination, the calcination time is 24 hours, then cooled to room temperature at a cooling rate of 1-10 ℃/min, and the obtained calcined product is ground to obtain the cation modified lithium nickel manganese oxide spinel positive electrode material with high energy density. The inventors found that in the above preferred case, it is possible to grow the product structure more sufficiently and avoid oxygen deficiency of the product and impurity phase generation to affect the uniformity and performance of the product.
In the invention, the calcination operation is preferably performed in a muffle furnace, and the specific temperature rising process is as follows: and (3) starting from room temperature, raising the temperature at a constant speed according to the temperature raising rate, and maintaining after reaching the calcining temperature.
The inventor finds that under the preferred embodiment, the cation modified high-energy density lithium nickel manganese oxide spinel anode material prepared by the method provided by the invention has good cycle stability and rate capability, and the preparation method has the advantages of simple process, convenient operation, low cost and easy industrialization.
As previously described, a third aspect of the present invention provides the use of the cation modified high energy density lithium nickel manganese oxide spinel cathode material of the first aspect described above in a cathode material for a lithium ion battery.
The invention will be described in detail below by way of examples.
In the following examples, unless otherwise specified, the experimental apparatus and the raw materials involved are commercially available.
Experimental instrument:
battery test system: CT-4008Tn, shenzhen New Will electronics Co., ltd;
box type high temperature sintering furnace: KSL-1200X, synechocystalline materials technologies Co., ltd;
planetary ball mill: pulverisette6, FRITSCH, germany;
defoaming mixer: AR100, THINKY Co., japan.
Raw materials:
lithium carbonate: 65175B-500g, aladin Co;
nickel oxide: a13071-100g, western reagent;
manganese dioxide: m813969-250g, michelin Corp;
ferroferric oxide: i811859-100g, michelia Corp;
tricobalt tetraoxide: c111617-100g, aladin Co;
gallium oxide: a49357-25g, innochem;
polypropylene microporous membrane: celgard2500/25 μm, celgard company, USA.
Example 1
The preparation method of the high-energy-density lithium nickel manganese oxide spinel anode material S1 without cationic modification, which is marked as LNMO, comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel oxide and 2.6345g of manganese dioxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the addition amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) Placing the mixed precursor obtained in the step (1) in a muffle furnace, heating the mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere for first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, grinding, heating to 700 ℃ at a heating rate of 5 ℃/min for second calcination, cooling to room temperature at a cooling rate of 5 ℃/min, and grinding the obtained calcined product to obtain the black positive electrode material S1 of the lithium nickel manganese oxide spinel with high energy density and without cationic modification.
The battery was assembled and tested as follows:
(1) Uniformly mixing the obtained high-energy-density lithium nickel manganese oxide spinel anode material S1 without cationic modification with acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, mixing and stirring for 20 minutes in a deaerator to obtain uniformly dispersed slurry, coating the obtained slurry on a carbon-coated aluminum foil, and vacuum drying at 105 ℃ for 12 hours, and then cutting into round electrode plates with the diameter of 10 mm.
(2) 1mol/L LiPF6 is used as electrolyte, a polypropylene microporous membrane (Celgard 2500) is used as a diaphragm, a metal lithium sheet is used as a reference electrode, and a CR2032 button cell is prepared from the material in a glove box filled with argon;
(3) And at 25 ℃, constant current charge and discharge testing and multiplying power testing are carried out on the button cell by using a CT-4008Tn cell testing system of Shenzhen New wile electronic limited company, wherein the testing voltage range is 1.5V-4.97V.
Example 2
Preparation of cation modified high energy density lithium nickel manganese oxide spinel cathode material S2, denoted LNMO-Fe 0.05 The preparation method comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel protoxide, 2.5467g of manganese dioxide and 0.0780g of ferroferric oxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the adding amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) And (3) placing the mixed precursor obtained in the step (1) in a muffle furnace, heating the mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere for first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, grinding, heating to 700 ℃ at a heating rate of 5 ℃/min for second calcination, and cooling to room temperature at a cooling rate of 5 ℃/min for 24 hours, and grinding the obtained calcined product to obtain the black positive electrode material S2 of the cation modified high-energy density lithium nickel manganese oxide spinel.
The battery was assembled and tested under the same conditions as in example 1.
Example 3
Preparation of cation modified high energy density lithium nickel manganese oxide spinel cathode material S3, denoted LNMO-Fe 0.3 The preparation method comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel oxide, 2.1076g of manganese dioxide and 0.4677g of ferroferric oxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the addition amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) And (3) placing the mixed precursor obtained in the step (1) in a muffle furnace, heating the mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere for first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, grinding, heating to 700 ℃ at a heating rate of 5 ℃/min for second calcination, and cooling to room temperature at a cooling rate of 5 ℃/min for 24 hours, and grinding the obtained calcined product to obtain the black positive electrode material S3 of the cation modified high-energy density lithium nickel manganese oxide spinel.
The battery was assembled and tested under the same conditions as in example 1.
Example 4
Preparation of cation modified high energy density lithium nickel manganese oxide spinel cathode material S4, denoted LNMO-Fe 0.45 Preparation methodThe method comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel protoxide, 1.8444g of manganese dioxide and 0.7016g of ferroferric oxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the addition amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) And (3) placing the mixed precursor in a muffle furnace, heating the obtained mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere to perform first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, performing second calcination after grinding, heating to 700 ℃ at a heating rate of 5 ℃/min, calcining for 24 hours, cooling to room temperature at a cooling rate of 5 ℃/min, and grinding the obtained calcined product to obtain the black cation modified high-energy density lithium nickel manganese oxide spinel anode material S4.
The battery was assembled and tested under the same conditions as in example 1.
Example 5
Preparation of cation modified high energy density lithium nickel manganese oxide spinel cathode material S5, denoted LNMO-Ga 0.05 The preparation method comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel protoxide, 2.5467g of manganese dioxide and 0.0937g of gallium oxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the addition amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) And (3) placing the mixed precursor in a muffle furnace, heating the obtained mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere to perform first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, performing second calcination after grinding, heating to 700 ℃ at a heating rate of 5 ℃/min, calcining for 24 hours, cooling to room temperature at a cooling rate of 5 ℃/min, and grinding the obtained calcined product to obtain the black cation modified high-energy density lithium nickel manganese oxide spinel anode material S2.
The battery was assembled and tested under the same conditions as in example 1.
Example 6
Preparation of cation modified high energy density lithium nickel manganese oxide spinel cathode material S6, denoted LNMO-Co 0.05 The preparation method comprises the following steps:
(1) 0.7837g of lithium carbonate, 0.7469g of nickel oxide, 2.5467g of manganese dioxide and 0.0803g of cobaltosic oxide are added into a planetary ball mill, absolute ethyl alcohol is used as a dispersion medium, the addition amount is 30mL, and the weight ratio of the ball materials is 5:1, ball milling for 8 hours at a rotational speed of 400 revolutions per minute, and fully mixing to obtain a mixed precursor;
(2) And (3) placing the mixed precursor in a muffle furnace, heating the obtained mixed precursor to 1000 ℃ at a heating rate of 5 ℃/min under an air atmosphere to perform first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 5 ℃/min, performing second calcination after grinding, heating to 700 ℃ at a heating rate of 5 ℃/min, calcining for 24 hours, cooling to room temperature at a cooling rate of 5 ℃/min, and grinding the obtained calcined product to obtain the black cation modified high-energy density lithium nickel manganese oxide spinel anode material S6.
The battery was assembled and tested under the same conditions as in example 1.
Example 7
The ferroferric oxide in example 2 was replaced with other metal compound Cr 2 O 3 、CeO 2 、Sm 2 O 3 、Nd 2 O 3 、In 2 O 3 、La 2 O 3 、ZrO 2 、Bi 2 O 3 Or Pr (Pr) 2 O 3 Lithium in lithium carbonate, nickel in nickel oxide, manganese in manganese dioxide, and the molar ratio of the amount of the metal element in the above metal compound is 1.05:0.5:1.45:0.05.
the preparation method of the material, the assembly of the battery and the test conditions were the same as in example 1.
The present invention was tested as follows for examples 1-7:
as shown in FIG. 1, the S1 obtained in the example 1 is analyzed by a scanning electron microscope, and the prepared spinel lithium nickel manganese oxide material is basically typical octahedron, the particle size is basically within 5 mu m, and the product consistency is good.
As shown in FIG. 2, the S2 obtained in the example 2 is subjected to scanning electron microscope analysis, and the prepared spinel lithium nickel manganese oxide material is basically a typical octahedron, has smaller particles compared with the S1, and has good product consistency.
As shown in fig. 3, XRD (X-ray diffraction) tests were performed on the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 2. The XRD patterns in examples 1 and 2 were found to be uniform, indicating that the proper doping of Fe did not alter the structure of the LNMO material. No other diffraction signal was observed on the XRD pattern other than the diffraction peak of the LNMO, indicating that Fe has entered the lattice of the LNMO material.
As shown in fig. 4, the lithium nickel manganese oxide spinel positive electrode materials obtained in examples 1 to 4 were subjected to a long-cycle test at a rate of 0.5C, and it was found that examples 2 to 4 exhibited more excellent cycle stability compared to example 1, wherein example 2 exhibited the best overall electrochemical performance.
As shown in fig. 5, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 2 were subjected to a charge-discharge curve test at a 0.2C magnification, and it was found that the phase transition of-2.7V plateau was suppressed after doping Fe, thereby improving the cycle stability.
As shown in fig. 6, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 2 were subjected to rate performance of 5 cycles at 0.2C, 0.5C, 1C, 2C, and 0.2C, and example 2 was found to have excellent rate performance.
As shown in fig. 7, energy density comparisons of 5 cycles at 0.2C, 0.5C, 1C, 2C, and 0.2C were made for the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 2, and it was found that example 1 and example 2 each had an energy density of > 900Wh/kg at 0.2C, except that example 2 had a higher energy density at other rates.
As shown in fig. 8, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 5 were subjected to a long-cycle test at a rate of 0.2C, and it was found that example 5 exhibited more excellent cycle stability as compared with example 1.
As shown in fig. 9, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 5 were subjected to a charge-discharge curve test at a 0.2C rate, and it was found that Ga doping inhibited the phase transition of-2.7V plateau, thereby improving the cycle stability.
As shown in fig. 10, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 6 were subjected to a long-cycle test at a rate of 0.2C, and it was found that example 6 exhibited more excellent cycle stability as compared with example 1.
As shown in fig. 11, the lithium nickel manganese oxide spinel positive electrode materials obtained in example 1 and example 6 were subjected to a charge-discharge curve test at a 0.2C rate, and it was found that Co doping inhibited the phase transition of-2.7V plateau, thereby improving the cycle stability.
As shown in Table 1, the lithium nickel manganese oxide spinel positive electrode materials obtained in examples 2-7 are subjected to element doping to compare the inhibition condition of-2.7V platform and the improvement condition of cycle stability, and different elements are found to have different effects, wherein Fe, ga and Co elements in examples 2, 5 and 6 have better inhibition effect on-2.7 platform when doped, so that the improvement of cycle stability of the lithium nickel manganese oxide spinel positive electrode materials is facilitated.
TABLE 1 comparison of elemental doping versus-2.7V plateau inhibition and versus improved cycling stability
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and other changes, modifications, substitutions, combinations and simplifications that do not depart from the spirit and principles of the invention are intended to be equivalent arrangements which are within the scope of the invention.
Claims (10)
1. A cationically modified high energy density lithium nickel manganese oxide spinel Dan Zheng pole material characterized by: the lithium nickel manganese oxide spinel positive electrode material has the following chemical general formula:
LiNi 0.5 Mn 1.5-x M x O 4 wherein M is Fe, co and/or Ga,0<x<0.5。
2. A cationically modified high energy density lithium nickel manganese oxide spinel Dan Zheng pole material according to claim 1, characterised in that: the nickel lithium manganate spinel positive electrode material reduces the cutoff voltage to 1.5V, and improves the specific discharge capacity, thereby realizing high energy density of more than 900 Wh/kg.
3. The method for preparing the cation modified high energy density lithium nickel manganese oxide spinel positive electrode material according to claim 1, which is characterized by comprising the following operation steps:
(1) Mixing a lithium source, a nickel source, a manganese source and an M source by adopting wet ball milling to obtain a mixed precursor;
(2) Heating the mixed precursor obtained in the step (1) to 1000 ℃ at a heating rate of 1-10 ℃/min for first calcination, wherein the calcination time is 12 hours, then cooling to room temperature at a cooling rate of 1-10 ℃/min, grinding, heating to 700 ℃ at a heating rate of 1-10 ℃/min for second calcination, wherein the calcination time is 24 hours, then cooling to room temperature at a cooling rate of 1-10 ℃/min, and grinding the obtained calcination product to obtain the cation modified lithium nickel manganese oxide spinel positive electrode material with high energy density.
4. A method of preparation according to claim 3, characterized in that: in the step (1), the lithium source is lithium carbonate, lithium hydroxide or lithium oxide, the nickel source is nickel oxide or nickel carbonate, and the manganese source is manganese dioxide or manganese carbonate; the M source is at least one of ferroferric oxide, cobaltosic oxide and gallium oxide.
5. A method of preparation according to claim 3, characterized in that: in the step (1), the lithium source is lithium carbonate, the nickel source is nickel oxide, and the manganese source is manganese dioxide.
6. A method of preparation according to claim 3, characterized in that: in the step (1), the molar ratio of the lithium source calculated as lithium element, the nickel source calculated as nickel element, the manganese source calculated as manganese element and the M source calculated as M element is (1.03-1.08): 0.5: y: x, wherein 0< x <0.5, y=1.5-x.
7. The method of manufacturing according to claim 6, wherein: the molar ratio of the lithium source calculated as lithium element, the nickel source calculated as nickel element, the manganese source calculated as manganese element and the M source calculated as M element is 1.05:0.5: y: x, wherein 0< x <0.5, y=1.5-x.
8. A method of preparation according to claim 3, characterized in that: and (3) adopting absolute ethyl alcohol or deionized water as a dispersion medium for the wet ball milling and mixing in the step (1).
9. A method of preparation according to claim 3, characterized in that: the ball weight ratio of the wet ball milling mixed materials adopted in the step (1) is 5:1-8:1, the ball milling rotating speed is 300-500 rpm, and the ball milling time is 6-10 hours.
10. The use of a cationically modified high energy density lithium nickel manganese oxide spinel positive electrode material according to claim 1 in power lithium batteries, consumer electronics lithium ion batteries.
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