CN110931770A - Cr-doped modified high-voltage spinel cathode material and preparation method thereof - Google Patents
Cr-doped modified high-voltage spinel cathode material and preparation method thereof Download PDFInfo
- Publication number
- CN110931770A CN110931770A CN201911218265.8A CN201911218265A CN110931770A CN 110931770 A CN110931770 A CN 110931770A CN 201911218265 A CN201911218265 A CN 201911218265A CN 110931770 A CN110931770 A CN 110931770A
- Authority
- CN
- China
- Prior art keywords
- salt
- cathode material
- lini
- spinel cathode
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 51
- 239000011029 spinel Substances 0.000 title claims abstract description 51
- 239000010406 cathode material Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 150000001844 chromium Chemical class 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 9
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002815 nickel Chemical class 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 13
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical group [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 10
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 10
- 229940071125 manganese acetate Drugs 0.000 claims description 10
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 10
- 229940078494 nickel acetate Drugs 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000004377 microelectronic Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000011572 manganese Substances 0.000 abstract description 44
- 239000011651 chromium Substances 0.000 abstract description 38
- 239000000463 material Substances 0.000 abstract description 21
- 239000007774 positive electrode material Substances 0.000 abstract description 18
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- 229910012406 LiNi0.5 Inorganic materials 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 229910013716 LiNi Inorganic materials 0.000 description 32
- 230000014759 maintenance of location Effects 0.000 description 15
- 238000012360 testing method Methods 0.000 description 14
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 5
- 239000000956 alloy Substances 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 235000011837 pasties Nutrition 0.000 description 4
- 238000010998 test method Methods 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910011657 LiCrxMn2−xO4 Inorganic materials 0.000 description 1
- 229910013198 LiNiMn Inorganic materials 0.000 description 1
- 229910003005 LiNiO2 Inorganic materials 0.000 description 1
- 229910016226 LixNi1-xO Inorganic materials 0.000 description 1
- 229910014279 LixNi1−xO Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Images
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/362—Composites
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a Cr-doped modified high-voltage spinel cathode material and a preparation method thereof, belonging to the technical field of lithium ion batteries. The synthesis method comprises the following steps: mixing lithium salt, nickel salt, manganese salt and chromium salt according to a certain proportion, adding deionized water to make the mixed raw materials into a paste, ball-milling and uniformly mixing to obtain a rheological phase, then drying, presintering to obtain a precursor, and finally calcining at high temperature and grinding to obtain LiNi0.5Mn1.5‑xCrxO4(x ═ 0, 0.01,0.03,0.06) is a modified spinel positive electrode material.The anode material prepared by the method has fine and uniform particles, smooth surface, good crystallization performance, higher specific discharge capacity and good rate performance; the doping can improve the cycle performance and the stability of the material structure, thereby having great industrial significance.
Description
Technical Field
The invention relates to a Cr-doped modified high-voltage spinel cathode material and a preparation method thereof, belonging to the technical field of lithium ion batteries.
Background
Since Li/LiCoO2Since batteries were first commercialized in japan, lithium ion batteries attracted much attention from researchers, and since 1991, many researchers considered lithium ion batteries as energy supply sources for electronic products including notebook computers, mobile phones, and some microelectronic products. Lithium cobaltate has the advantages of simpler synthesis method, high output voltage and the like, but the actual capacity is only half of the theoretical value, the price of cobalt is expensive, and importantly, cobalt has toxicity and is unfavorable for the environment.
In the whole research process of the lithium ion battery, the emphasis is to find a suitable positive active substance, a non-aqueous solvent and a spinel type positive material LiNi0.5Mn1.5O4Is a very promising cathode material because it has good thermal stability and is comparable to LiCoO2，LiNiO2Lower material cost and less pollution, however LiNi0.5Mn1.5O4The positive electrode material faces the problem of capacity decline in the circulation process, and particularly at high temperature, Mn element of the positive electrode material can be dissolved in an electrolyte solution to form NixO，LixNi1-xO, or (LiNiMn)xThe O-hetero phase causes oxygen defects in the spinel structure, thereby deteriorating the cycle performance. Therefore, there is an urgent need to provide an effective method for improving the LiNi of the spinel-type positive electrode material0.5Mn1.5O4The electrochemical performance of (2).
Disclosure of Invention
The invention provides a Cr-doped modified high-voltage spinel cathode material and a preparation method thereof, wherein the LiNi is replaced by Cr through element doping0.5Mn1.5O4Since Mn element in the positive electrode material has a stronger affinity for oxygen than Ni and Mn elements, LiNi doped with Cr element0.5Mn1.5O4The spinel cathode material has a more stable structure, reduces the polarization degree of an electrode, and remarkably improves the cycle performance of the lithium ion battery.
The invention aims to provide a preparation method of a Cr-doped modified high-voltage spinel cathode material, which comprises the following steps:
(1) mixing lithium salt, nickel salt, manganese salt and chromium salt according to a certain molar ratio, adding water into the mixture, and ball-milling for 2-5 h;
(2) and (2) drying the ball-milled mixture obtained in the step (1), pre-sintering the mixture at 400-600 ℃ for 6-9 hours to obtain a precursor, cooling and grinding the precursor, compacting the precursor, and calcining the precursor at 750-900 ℃ for 12-24 hours to obtain the product Cr-doped modified high-voltage spinel cathode material.
In one embodiment of the present invention, the lithium salt in step (1) is lithium acetate, the nickel salt is nickel acetate, the manganese salt is manganese acetate, and the chromium salt is chromium nitrate.
In one embodiment of the present invention, the molar ratio of the lithium salt, the nickel salt, the manganese salt and the chromium salt in step (1) is: 1:0.5:1.5: x, wherein x is more than or equal to 0 and less than or equal to 0.06.
In one embodiment of the present invention, the molar ratio of the lithium salt, the nickel salt, the manganese salt and the chromium salt in step (1) is: 1:0.5:1.5: x, wherein x is 0.01.
In one embodiment of the present invention, the ball milling time in step (1) is 2 hours or 5 hours.
In one embodiment of the present invention, the drying conditions in step (2) are: and drying the mixture in a blast drying oven at 80-120 ℃ for 10-15 hours.
In one embodiment of the present invention, the temperature of the drying in the step (2) is 80 ℃ or 120 ℃, and the time of the drying is 10 hours.
In one embodiment of the present invention, the temperature of the pre-sintering in the step (2) is 500 ℃ and the time is 8 hours.
In one embodiment of the present invention, the high temperature calcination in step (2) is performed at 800 ℃ for 12 hours.
The second purpose of the invention is to provide a Cr-doped modified high-voltage spinel cathode material, wherein the chemical general formula of the Cr-doped cathode material is LiNi0.5Mn1.5-xCrxO4Wherein x is between 0 and 0.06.
In the present inventionIn one embodiment of the invention, the LiNi is0.5Mn1.5-xCrxO4Wherein x has a value of 0, 0.01,0.03, 0.06.
In one embodiment of the present invention, the LiNi is0.5Mn1.5-xCrxO4Wherein x has a value of 0.01.
The third purpose of the invention is to provide a new energy automobile battery, which applies the Cr-doped modified high-voltage spinel cathode material.
The fourth purpose of the invention is to provide the application of the Cr-doped modified high-voltage spinel cathode material in the field of microelectronic products.
The invention has the beneficial effects that:
(1) the anode material prepared by the invention has smooth surface, good crystallinity and smaller particles, and improves the structural stability of the material.
(2) The anode material prepared by the invention has the advantages of excellent electrochemical performance, high capacity, good cycle performance and obviously improved rate performance and coulombic efficiency.
(3) The anode material prepared by the invention is of a spinel structure, the preparation method is simple and feasible, the raw material reserves are rich, the price is low, and the anode material is a product which has an application prospect and can be industrialized.
Drawings
FIG. 1 shows LiNi, a spinel positive electrode material in examples 1 to 40.5Mn1.5-xCrxO4(x is 0, 0.01,0.03, 0.06).
FIG. 2 shows LiNi, a spinel positive electrode material in examples 1 to 40.5Mn1.5-xCrxO4(x ═ 0, 0.01,0.03,0.06) cycle profile at 25 ℃ at 0.2C.
FIG. 3 shows LiNi, a spinel positive electrode material in examples 1 to 40.5Mn1.5-xCrxO4(x is 0, 0.01,0.03,0.06) at 25 ℃, under different multiplying power.
FIG. 4 shows LiNi, a spinel positive electrode material in examples 1 to 40.5Mn1.5-xCrxO4(x＝0，0.01,0.03,0.06) cycle profile at 55 ℃ at 0.2C.
FIG. 5 Positive electrode Material LiNi prepared in example 20.5Mn1.49Cr0.01O4EDS map of (a).
FIG. 6 shows LiNi, a spinel positive electrode material in examples 1 to 40.5Mn1.5-xCrxO4(x ═ 0, 0.01,0.03, 0.06).
Detailed Description
For a better understanding of the present invention, the following further illustrates the contents of the invention with reference to examples, but the contents of the invention are not limited to the examples given below.
Example 1 preparation of spinel cathode Material LiNi0.5Mn1.5O4And testing the electrical properties of the material
(1) Mixing 6.1212g of lithium acetate, 7.6176g of nickel acetate and 22.2809g of manganese acetate, namely the molar ratio of the lithium acetate to the nickel acetate to the manganese acetate is 1:0.5:1.5, adding 5ml of deionized water into the mixture, adding water, fully and uniformly stirring to enable the mixed raw materials to be pasty, and carrying out ball milling for 5 hours;
(2) drying the ball-milled mixture in the step (1) in a forced air drying oven at 80 ℃ for 10 hours to evaporate and drive off the solvent to obtain a solid-phase product; placing the solid-phase product in a muffle furnace for calcining, wherein the heating rate is 5 ℃/min, the heating is carried out to 500 ℃, and the calcining is carried out for 8 hours, so as to obtain a precursor; cooling the precursor to room temperature, grinding the precursor in a mortar machine for 1 hour, compacting the ground precursor, putting the compacted precursor in a muffle furnace, calcining the compacted precursor in air atmosphere at the temperature rise speed of 5 ℃/min to 800 ℃, calcining the compacted precursor for 12 hours, and cooling the compacted precursor to room temperature to obtain the spinel anode material LiNi of the lithium ion battery0.5Mn1.5O4。
(3) Assembly and electrical performance testing of the cells:
the method for assembling and testing the electrical properties of the battery is described in the literature "Sol-gel assisted high temperature ball milling Synthesis LiCrxMn2-xO4Section 1.3, published in 5.2017, vol.38, vol.5 of university of northeast.
LiNi serving as spinel cathode material0.5Mn1.5O4The initial charge-discharge curve of the assembled half-cell under the charge-discharge conditions of the test voltage of 3.5-5.1V and 0.2C is shown in figure 1, and as can be seen from figure 1, the initial discharge specific capacity of the anode material at room temperature is 128.5 mAh.g-1。
LiNi serving as spinel cathode material0.5Mn1.5O4The discharge curve of the assembled half-cell after 50 cycles at 0.2C is shown in figure 2, and as can be seen from figure 2, the specific discharge capacity of the cathode material after 50 cycles is 127.5mAh g-1The capacity retention rate was 98.6%.
LiNi serving as spinel cathode material0.5Mn1.5O4The discharge specific capacity cycling curve chart of the assembled half-cell under different current densities is shown in FIG. 3, and it can be seen from FIG. 3 that under the condition of high multiplying power 5C, after 10 cycles, the positive electrode material LiNi0.5Mn1.5O4The specific discharge capacity of the alloy is 36.5mAh g-1The capacity retention rate was 71.2%. When the temperature returns to 0.2C, the capacity retention rate and the specific discharge capacity of the material are not much different from those of the material measured at 0.2C for the first time, which shows that the structure of the material is not damaged at the high rate of 5C before and after doping.
LiNi serving as spinel cathode material0.5Mn1.5O4The room temperature discharge curve of the assembled half cell is shown in figure 4 after 50 times of circulation at 55 ℃ under 0.2 ℃, and the specific discharge capacity of the positive electrode after 50 times of circulation at 55 ℃ is 113.3mAh g can be seen from figure 4-1The capacity retention rate reaches 85.5%.
Example 2 preparation of spinel cathode Material LiNi0.5Mn1.49Cr0.01O4
(1) Mixing 6.1212g of lithium acetate, 7.6176g of nickel acetate, 22.1324g of manganese acetate and 0.2425g of chromium nitrate, wherein the molar ratio of the lithium acetate to the nickel acetate to the manganese acetate is 1:0.5:1.5:0.01, adding 5ml of deionized water into the mixture to enable the mixed raw materials to be pasty, and carrying out ball milling for 5 hours;
(2) step (2) was performed in the same manner as in example 1 to prepare a lithium ion batterySpinel cathode material LiNi0.5Mn1.49Cr0.01O4。
(3) Qualitative analysis is carried out on Be-U elements in a micro-area of a sample through an X-ray energy spectrometer (EDS for short), and after X-rays enter a lithium drift silicon detector, electron-hole pairs are generated in crystals. At low temperature, the average consumed energy for generating one electron-hole pair is 3.8ev, the electron-hole pair forms a voltage pulse signal, and the height of the voltage pulse output by the detector corresponds to the energy of the X-ray. In this example, a Noran System Six EDS made in america was selected to analyze the elemental composition of the sample, and the distribution of the elements was observed, and the acceleration voltage was 20K. FIG. 5 shows the LiNi as the positive electrode material0.5Mn1.49Cr0.01O4The EDS diagram of (a) can be seen from fig. 5: the peak formed by the Cr element is obvious, and shows that the Cr element is successfully doped into the crystal lattice of the spinel material.
(4) Electrical properties of the test materials:
the prepared cathode material is assembled into a CR2032 type button cell to carry out charge-discharge cycle test, and the test method is the same as that of the example 1.
LiNi serving as spinel cathode material0.5Mn1.49Cr0.01O4The initial charge-discharge curve of the assembled half-cell under the charge-discharge conditions of the test voltage of 3.5-5.1V and 0.2C is shown in figure 1, and as can be seen from figure 1, the initial discharge specific capacity of the anode material at room temperature is 133.5 mAh.g-1。
LiNi serving as spinel cathode material0.5Mn1.49Cr0.01O4The discharge curve of the assembled half-cell after 50 cycles at 0.2C is shown in FIG. 2, and as can be seen from FIG. 2, the specific discharge capacity of the cathode material after 50 cycles is 133.2mAh g-1The capacity retention rate was 99.8%.
LiNi serving as spinel cathode material0.5Mn1.49Cr0.01O4The discharge specific capacity cycling curve chart of the assembled half-cell under different current densities is shown in FIG. 3, and it can be seen from FIG. 3 that under the condition of high multiplying power 5C, after 10 cycles, the positive electrode material LiNi0.5Mn1.49Cr0.01O4The specific discharge capacity of the alloy is 78.6 mAh.g-1The capacity retention rate was 98.2%. When the temperature returns to 0.2C, the capacity retention rate and the specific discharge capacity of the material are not much different from those of the material measured at 0.2C for the first time, which shows that the structure of the material is not damaged at the high rate of 5C before and after doping.
LiNi serving as spinel cathode material0.5Mn1.49Cr0.01O4The room temperature discharge curve of the assembled half-cell is shown in figure 4 after 50 times of circulation at 55 ℃ under 0.2 ℃, and the specific discharge capacity of the positive electrode after 50 times of circulation at 55 ℃ is 131.9mAh g as shown in figure 4-1The capacity retention rate reaches 98.5%.
Example 3 preparation of spinel cathode material LiNi0.5Mn1.47Cr0.03O4
(1) Mixing 6.1212g of lithium acetate, 7.6176g of nickel acetate, 21.8353g of manganese acetate and 0.7275g of chromium nitrate, wherein the molar ratio of the lithium acetate to the nickel acetate to the manganese acetate is 1:0.5:1.5:0.03, adding 5ml of deionized water into the mixture to enable the mixed raw materials to be pasty, and carrying out ball milling for 5 hours;
(2) step (2) is the same as example 1, and the spinel cathode material LiNi of the lithium ion battery is prepared0.5Mn1.47Cr0.03O4。
(3) Electrical properties of the test materials:
the prepared cathode material is assembled into a CR2032 type button cell to carry out charge-discharge cycle test, and the test method is the same as that of the example 1.
LiNi serving as spinel cathode material0.5Mn1.47Cr0.03O4The initial charge-discharge curve of the assembled half-cell under the charge-discharge conditions of the test voltage of 3.5-5.1V and 0.2C is shown in figure 1, and as can be seen from figure 1, the initial discharge specific capacity of the anode material at room temperature is 128.8 mAh.g-1。
LiNi serving as spinel cathode material0.5Mn1.47Cr0.03O4The assembled half-cell, 50 cycles at 0.2C, discharge curve is shown in FIG. 2, and as can be seen from FIG. 2, the positiveThe specific discharge capacity of the electrode material after 50 cycles is 127.2 mAh.g-1The capacity retention rate was 98.7%.
LiNi serving as spinel cathode material0.5Mn1.47Cr0.03O4The discharge specific capacity cycling curve chart of the assembled half-cell under different current densities is shown in FIG. 3, and it can be seen from FIG. 3 that under the condition of high multiplying power 5C, after 10 cycles, the positive electrode material LiNi0.5Mn1.5O4The specific discharge capacity of the alloy is 75.5 mAh.g-1The capacity retention rate is 97.8%, and the capacity retention rate and the specific discharge capacity of the material when the material returns to 0.2C are not much different from those when the material is measured at 0.2C for the first time, which shows that the material structure is not damaged at the high rate of 5C before and after doping.
LiNi serving as spinel cathode material0.5Mn1.47Cr0.03O4The room temperature discharge curve of the assembled half cell is shown in figure 4 after 50 times of circulation at 55 ℃ under 0.2 ℃, and the specific discharge capacity of the positive electrode after 50 times of circulation at 55 ℃ is 124.2 mAh.g-1The capacity retention rate reaches 95.5%.
Example 4 preparation of spinel cathode Material LiNi0.5Mn1.44Cr0.06O4
(1) Mixing 6.1212g of lithium acetate, 7.6176g of nickel acetate, 21.3897g of manganese acetate and 1.4551g of chromium nitrate, wherein the molar ratio of the lithium acetate to the nickel acetate to the manganese acetate is 1:0.5:1.5:0.06, adding 5ml of deionized water into the mixture to enable the mixed raw materials to be pasty, and carrying out ball milling for 5 hours;
(2) step (2) is the same as example 1, and the spinel cathode material LiNi of the lithium ion battery is prepared0.5Mn1.44Cr0.06O4。
(3) Electrical properties of the test materials:
the prepared cathode material is assembled into a CR2032 type button cell to carry out charge-discharge cycle test, and the test method is the same as that of the example 1.
LiNi serving as spinel cathode material0.5Mn1.44Cr0.06O4Assembled half cell, under testThe first charge-discharge curve under the charge-discharge conditions of the voltage of 3.5-5.1V and the temperature of 0.2C is shown in figure 1, and as can be seen from figure 1, the first discharge specific capacity of the cathode material at room temperature is 125.3 mAh.g-1。
LiNi serving as spinel cathode material0.5Mn1.44Cr0.06O4The discharge curve of the assembled half-cell after 50 cycles at 0.2C is shown in FIG. 2, and as can be seen from FIG. 2, the specific discharge capacity of the cathode material after 50 cycles is 124.7mAh g-1The capacity retention rate was 99.5%.
LiNi serving as spinel cathode material0.5Mn1.44Cr0.06O4The discharge specific capacity cycling curve chart of the assembled half-cell under different current densities is shown in FIG. 3, and it can be seen from FIG. 3 that under the condition of high multiplying power 5C, after 10 cycles, the positive electrode material LiNi0.5Mn1.44Cr0.06O4The specific discharge capacity of the alloy is 69.1mAh g-1The capacity retention rate was 97.2%.
LiNi serving as spinel cathode material0.5Mn1.44Cr0.06O4The room temperature discharge curve of the assembled half-cell is shown in figure 4 after 50 times of circulation at 55 ℃ under 0.2 ℃, and the specific discharge capacity of the positive electrode is 121.6mAh g after 50 times of circulation at 55 ℃ as can be seen from figure 4-1The capacity retention rate reaches 95.1%.
Example 5XRD testing
XRD tests were carried out on the spinel positive electrode materials of examples 1 to 4, respectively, and FIG. 6 shows LiNi0.5Mn1.5-xCrxO4(0. ltoreq. x. ltoreq.0.06) XRD pattern of spinel positive electrode material, as can be seen from FIG. 6, there are no peaks at 37.5 deg.C, 43.6 deg.C and 63.3 deg.C, indicating that Ni is not generatedxO、LixNi1-xO-impurity phase, main diffraction peak and LiNi after doping Cr element0.5Mn1.5O4The peak shapes are approximately the same, which shows that the crystal structure of the material doped with Cr element is not changed into other crystal structures, and the diffraction peak intensity of the sample is higher, thus showing that the crystallization state of the material is good.
Although the present invention has been described with reference to the preferred embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. The preparation method of the Cr-doped modified high-voltage spinel cathode material is characterized by comprising the following steps of:
(1) mixing lithium salt, nickel salt, manganese salt and chromium salt according to a certain molar ratio, adding water into the mixture, and ball-milling for 2-5 h;
(2) and (2) drying the ball-milled mixture obtained in the step (1), pre-sintering the mixture at 400-600 ℃ for 6-9 hours to obtain a precursor, cooling and grinding the precursor, compacting the precursor, and calcining the precursor at 750-900 ℃ for 12-24 hours to obtain the product Cr-doped modified high-voltage spinel cathode material.
2. The method according to claim 1, wherein the lithium salt in step (1) is lithium acetate, the nickel salt is nickel acetate, the manganese salt is manganese acetate, and the chromium salt is chromium nitrate.
3. The preparation method according to claim 1, wherein the molar ratio of the lithium salt, the nickel salt, the manganese salt and the chromium salt in step (1) is as follows: 1:0.5:1.5: x, wherein x is more than or equal to 0 and less than or equal to 0.06.
4. The preparation method according to claim 1, wherein the molar ratio of the lithium salt, the nickel salt, the manganese salt and the chromium salt in step (1) is as follows: 1:0.5:1.5: x, wherein x is 0.01.
5. The method according to claim 1, wherein the temperature of the pre-sintering in the step (2) is 500 ℃ and the time is 8 hours.
6. The method according to claim 1, wherein the high-temperature calcination in step (2) is carried out at a temperature of 800 ℃ for 12 hours.
7. The production method according to claim 1, wherein the rate of temperature increase in the pre-sintering and high-temperature calcination in the step (2): 3-8 ℃/min.
8. The Cr-doped modified high-voltage spinel cathode material obtained by the method of any one of claims 1 to 7.
9. A new energy automobile battery is characterized in that the Cr-doped modified high-voltage spinel cathode material disclosed in claim 7 is applied.
10. Use of the Cr-doped modified high voltage spinel cathode material of claim 7 in the field of microelectronic products.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911218265.8A CN110931770A (en) | 2019-12-03 | 2019-12-03 | Cr-doped modified high-voltage spinel cathode material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911218265.8A CN110931770A (en) | 2019-12-03 | 2019-12-03 | Cr-doped modified high-voltage spinel cathode material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110931770A true CN110931770A (en) | 2020-03-27 |
Family
ID=69848442
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911218265.8A Pending CN110931770A (en) | 2019-12-03 | 2019-12-03 | Cr-doped modified high-voltage spinel cathode material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110931770A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112582601A (en) * | 2020-12-14 | 2021-03-30 | 中钢集团南京新材料研究院有限公司 | Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide |
| CN113149610A (en) * | 2021-04-07 | 2021-07-23 | 北京高压科学研究中心 | Preparation method of spinel type lithium battery positive electrode ceramic material based on interface regulation |
| CN114122381A (en) * | 2021-11-22 | 2022-03-01 | 江南大学 | MnO (MnO)2Coated LiNi0.5Mn1.5O4Positive electrode material and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709546A (en) * | 2012-06-12 | 2012-10-03 | 浙江南都电源动力股份有限公司 | Method for producing high voltage anode material LiNi 0.5 Mn 1.5O4 of lithium ion battery |
| CN103700840A (en) * | 2014-01-08 | 2014-04-02 | 山东精工电子科技有限公司 | Cathode material of high-voltage lithium battery and preparation method for cathode material |
| CN105206811A (en) * | 2015-09-23 | 2015-12-30 | 中信国安盟固利电源技术有限公司 | Wrapped and modified anode material doped with metallic oxide and preparation method of anode material |
| CN105576231A (en) * | 2016-02-25 | 2016-05-11 | 江南大学 | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material |
| JP2016162719A (en) * | 2015-03-05 | 2016-09-05 | 住友金属鉱山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
-
2019
- 2019-12-03 CN CN201911218265.8A patent/CN110931770A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102709546A (en) * | 2012-06-12 | 2012-10-03 | 浙江南都电源动力股份有限公司 | Method for producing high voltage anode material LiNi 0.5 Mn 1.5O4 of lithium ion battery |
| CN103700840A (en) * | 2014-01-08 | 2014-04-02 | 山东精工电子科技有限公司 | Cathode material of high-voltage lithium battery and preparation method for cathode material |
| JP2016162719A (en) * | 2015-03-05 | 2016-09-05 | 住友金属鉱山株式会社 | Positive electrode active material for nonaqueous electrolyte secondary battery and nonaqueous electrolyte secondary battery using the same |
| CN105206811A (en) * | 2015-09-23 | 2015-12-30 | 中信国安盟固利电源技术有限公司 | Wrapped and modified anode material doped with metallic oxide and preparation method of anode material |
| CN105576231A (en) * | 2016-02-25 | 2016-05-11 | 江南大学 | High-voltage lithium oil battery positive electrode material with spinel structure and preparation method of high-voltage lithium oil battery positive electrode material |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112582601A (en) * | 2020-12-14 | 2021-03-30 | 中钢集团南京新材料研究院有限公司 | Method for preparing lithium nickel manganese oxide by utilizing waste lithium manganese oxide and lithium nickel manganese oxide |
| CN113149610A (en) * | 2021-04-07 | 2021-07-23 | 北京高压科学研究中心 | Preparation method of spinel type lithium battery positive electrode ceramic material based on interface regulation |
| CN114122381A (en) * | 2021-11-22 | 2022-03-01 | 江南大学 | MnO (MnO)2Coated LiNi0.5Mn1.5O4Positive electrode material and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109873140B (en) | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material | |
| CN104868122A (en) | Preparation method of single-crystal Li(NiCoMn)O2 ternary cathode material | |
| CN107069020A (en) | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN106450211A (en) | Surface-coated composite lithium-rich manganese-based cathode material and preparation method thereof | |
| CN103762354A (en) | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery | |
| CN108091854A (en) | A kind of high-voltage spinel type anode material for lithium-ion batteries of Anion-cation multiple dope and preparation method thereof | |
| CN105742601A (en) | Method for in-situ synthesis of carbon coated-hydrated V3O7 nanobelt and lithium ion battery | |
| CN110931770A (en) | Cr-doped modified high-voltage spinel cathode material and preparation method thereof | |
| CN112510200A (en) | Preparation method of lithium-rich manganese-based material coated by double conductive layers | |
| CN107768628B (en) | Lithium ion battery anode material and preparation method thereof | |
| CN105489883A (en) | Preparing method for rapidly obtaining ternary anode material of lithium ion battery and anode material | |
| CN105185969B (en) | A kind of positive electrode and preparation method thereof | |
| CN114843459B (en) | Antimony pentasulfide-based material and preparation method and application thereof | |
| CN110921720B (en) | High-voltage lithium ion battery positive electrode material and preparation method thereof | |
| CN114203993B (en) | Li (lithium ion battery) 2 SeO 4 Fast ion conductor modified lithium ion battery anode material | |
| CN117012925A (en) | Rare earth metal or transition metal doped lithium molybdate/carbon composite material, and preparation method and application thereof | |
| CN116081710A (en) | Potassium-doped nickel-manganese-copper ternary layered oxide and preparation method and application thereof | |
| CN114639813A (en) | Vanadium B-site doped pyrochlore type poly-antimonic acid material and preparation method and application thereof | |
| CN115092962A (en) | Molybdenum dioxide/carbon composite electrode material and preparation method and application thereof | |
| CN111653765A (en) | Preparation method of niobium-doped nickel-cobalt lithium aluminate anode material | |
| CN112490436A (en) | Preparation method of nickel-doped spinel lithium manganate serving as lithium ion battery anode material | |
| CN108123131B (en) | Preparation method of ternary nano single crystal cathode material of lithium ion battery | |
| CN105024070A (en) | Preparation method of lithium titanium silicate anode material for lithium ion battery | |
| CN111470544A (en) | Solid-phase sintering method of carbon-coated ferroferric oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200327 |