CN114975985A - Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery - Google Patents

Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery Download PDF

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CN114975985A
CN114975985A CN202210758193.1A CN202210758193A CN114975985A CN 114975985 A CN114975985 A CN 114975985A CN 202210758193 A CN202210758193 A CN 202210758193A CN 114975985 A CN114975985 A CN 114975985A
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source
temperature
cathode material
sintering
doped high
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吴昌栩
罗奕沅
黄建平
黄珺辰
余锦华
王伟立
黄志忠
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Sanming New Energy Industry Technology Research Institute Co ltd
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Abstract

The application provides a Ti-Cr co-doped high-voltage spinel cathode material, a preparation method thereof, a lithium ion battery anode and a lithium ion battery. The Ti-Cr co-doped high-voltage spinel cathode material has a chemical formula of LiNi 0.5‑x Mn 1.5‑y Ti x Cr y O 4 . The preparation method comprises the following steps: mixing raw materials including lithium source, nickel source, manganese source, titanium source, chromium source, solvent and dispersantMixing the materials to obtain slurry; drying the slurry to obtain solid powder, and then pre-sintering the solid powder to obtain a precursor; and carrying out secondary sintering on the precursor to obtain the Ti-Cr co-doped high-voltage spinel cathode material. The Ti-Cr co-doped high-pressure spinel cathode material provided by the application carries out substitution doping on Ni and Mn elements through Ti elements and Cr elements, so that the structural strength of the material is enhanced, and the stability of the material in a long-time circulation process is effectively improved.

Description

Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery
Technical Field
The application relates to the field of lithium ion batteries, in particular to a Ti-Cr co-doped high-voltage spinel cathode material, a preparation method thereof, a lithium ion battery cathode and a lithium ion battery.
Background
With the rapid development of new energy industries, lithium battery devices gradually enter people's daily life. Research on the positive electrode material is also gradually progressing toward high operating voltage and high energy density to meet different use demands of consumers. High voltage spinel LiNi relative to other positive electrode materials 0.5 Mn 1.5 O 4 The positive electrode material has advantages such as a high operating voltage (about 4.7V) and a high energy density (650Wh/kg), and is considered to be an ideal next-generation positive electrode material. However, high pressure spinel LiNi 0.5 Mn 1.5 O 4 The John-Teller effect of the anode material in the synthesis process and the defects of the transition metal Mn such as dissolution, unstable structure and the like under the high-voltage working condition influence the performance of the battery.
Disclosure of Invention
The application aims to provide a Ti-Cr co-doped high-voltage spinel cathode material, a preparation method thereof, a lithium ion battery cathode and a lithium ion battery, so as to solve the problems.
In order to achieve the purpose, the following technical scheme is adopted in the application:
a Ti-Cr co-doped high-voltage spinel cathode material has a chemical formula of LiNi 0.5-x Mn 1.5-y Ti x Cr y O 4 Wherein x is more than or equal to 0.001 and less than or equal to 0.06, and y is more than or equal to 0.001 and less than or equal to 0.07.
The application also provides a preparation method of the Ti-Cr co-doped high-voltage spinel cathode material, which comprises the following steps:
mixing raw materials including a lithium source, a nickel source, a manganese source, a titanium source, a chromium source, a solvent and a dispersant to obtain slurry;
drying the slurry to obtain solid powder, and then pre-sintering the solid powder to obtain a precursor;
and carrying out secondary sintering on the precursor to obtain the Ti-Cr co-doped high-voltage spinel cathode material.
Preferably, the lithium source comprises one or more of lithium carbonate, lithium acetate, lithium nitrate;
the nickel source comprises nickel oxide and/or nickel acetate tetrahydrate;
the manganese source comprises one or more of manganese oxide, manganese dioxide and mangano-manganic oxide;
the titanium source comprises titanium monoxide and/or titanium dioxide;
the chromium source comprises chromium dioxide and/or chromium sesquioxide;
the solvent comprises absolute ethyl alcohol;
the dispersant comprises isopropanol and/or polyvinylpyrrolidone, and the dosage of the dispersant is 1 wt% of the slurry.
Preferably, the mixing is followed by ball milling;
the ball-milling ball material mass ratio is (60-90): 1, the rotating speed is 500-650r/min, and the time is 4-5 h.
Preferably, the drying temperature is 100-120 ℃, and the drying time is 4-5 h.
Preferably, the presintering atmosphere is air;
the temperature rising procedure of the pre-sintering is as follows: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min at 100-500 ℃, the heating rate is 1-2 ℃/min at 400-500 ℃, the temperature-rising end point temperature is 500-.
Preferably, the temperature rise procedure of the secondary sintering is as follows: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min between 100 ℃ and 850 ℃, the heating rate is 1-2 ℃/min between 850 ℃ and 950 ℃, the temperature of the heating end point is 900-.
Preferably, the secondary sintering is further followed by crushing and separation;
the screen mesh used for separation is 200 meshes, and undersize materials are taken.
The application also provides a lithium ion battery anode, and the raw material of the lithium ion battery anode comprises the Ti-Cr co-doped high-voltage spinel anode material.
The application also provides a lithium ion battery, which comprises the lithium ion battery anode.
Compared with the prior art, the beneficial effect of this application includes:
the Ti-Cr co-doped high-pressure spinel cathode material provided by the application is characterized in that Ni and Mn are substituted and doped by Ti elements and Cr elements, and the Ti-Cr elements are co-doped in a synergistic effect, so that the structural distortion of the material caused by the John-Telle effect in the preparation process is reduced, the dissolution of transition metal in the circulation process and the electrode/electrolyte interface side reaction are relieved, the structural strength of the material is enhanced, and the stability of the material in the long-time circulation process is effectively improved.
According to the preparation method of the Ti-Cr co-doped high-pressure spinel cathode material, the dispersing agent is added in the preparation process for dispersing treatment, so that the uniformity of mixed materials is improved; the method has the advantages of good process stability, safe and controllable preparation process, simple preparation process and good industrialization prospect.
The lithium ion battery anode and the lithium ion battery provided by the application have good cycle performance.
Drawings
To more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are required to be used in the embodiments are briefly described below, and it should be understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered as limiting the scope of the present application.
FIG. 1 is a first-turn charge-discharge curve at 30 ℃ and 0.2 ℃ of example 3, comparative example 1 and comparative example 2;
FIG. 2 is a graph of 300 cycles at 30 ℃ and 1C for example 3 and comparative examples 1 and 2;
FIG. 3 is a cycle performance curve of example 3 and comparative examples 1 and 2 at different magnifications at 60 ℃;
fig. 4 is an SEM image of the Ti — Cr element co-doped high voltage spinel cathode material obtained in example 3.
Detailed Description
The term as used herein:
"prepared from … …" is synonymous with "comprising". The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
The conjunction "consisting of … …" excludes any unspecified elements, steps or components. If used in a claim, the phrase is intended to claim as closed, meaning that it does not contain materials other than those described, except for the conventional impurities associated therewith. When the phrase "consisting of … …" appears in a clause of the subject matter of the claims rather than immediately after the subject matter, it defines only the elements described in the clause; other elements are not excluded from the claims as a whole.
When an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, when the range "1 ~ 5" is disclosed, the ranges described should be construed to include the ranges "1 ~ 4", "1 ~ 3", "1 ~ 2 and 4 ~ 5", "1 ~ 3 and 5", and the like. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In these examples, the parts and percentages are by mass unless otherwise indicated.
"part by mass" means a basic unit of measure indicating a mass ratio of a plurality of components, and 1 part may represent any unit mass, for example, 1g or 2.689 g. If we say that the part by mass of the component A is a part by mass and the part by mass of the component B is B part by mass, the ratio of the part by mass of the component A to the part by mass of the component B is a: b. alternatively, the mass of the A component is aK and the mass of the B component is bK (K is an arbitrary number, and represents a multiple factor). It is unmistakable that, unlike the parts by mass, the sum of the parts by mass of all the components is not limited to 100 parts.
"and/or" is used to indicate that one or both of the illustrated conditions may occur, e.g., a and/or B includes (a and B) and (a or B).
A Ti-Cr co-doped high-voltage spinel cathode material has a chemical formula of LiNi 0.5-x Mn 1.5-y Ti x Cr y O 4 Wherein x is more than or equal to 0.001 and less than or equal to 0.06, and y is more than or equal to 0.001 and less than or equal to 0.07.
Alternatively, x may be any value between 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, or 0.001-0.06; y may be 0.001, 0.005, 0.01, 0.02, 0.03, 0.04, 0.05, 0.06, 0.07, or any value between 0.001 and 0.07.
The application also provides a preparation method of the Ti-Cr co-doped high-voltage spinel cathode material, which comprises the following steps:
mixing raw materials including a lithium source, a nickel source, a manganese source, a titanium source, a chromium source, a solvent and a dispersant to obtain slurry;
drying the slurry to obtain solid powder, and then pre-sintering the solid powder to obtain a precursor;
and carrying out secondary sintering on the precursor to obtain the Ti-Cr co-doped high-pressure spinel cathode material.
In an alternative embodiment, the lithium source comprises one or more of lithium carbonate, lithium acetate, lithium nitrate;
in an alternative embodiment, the nickel source comprises nickel oxide and/or nickel acetate tetrahydrate;
in an alternative embodiment, the manganese source comprises one or more of manganese oxide, manganese dioxide, trimanganese tetroxide;
in an alternative embodiment, the titanium source comprises titanium monoxide and/or titanium dioxide;
in an alternative embodiment, the chromium source comprises chromium dioxide and/or chromium oxide;
in an alternative embodiment, the solvent comprises absolute ethanol;
in an alternative embodiment, the dispersant comprises isopropyl alcohol and/or polyvinylpyrrolidone, and is used in an amount of 1 wt% of the slurry.
In an alternative embodiment, the mixing further comprises ball milling;
in an alternative embodiment, the ball-milled balls have a mass ratio of (60-90): 1, the rotating speed is 500-650r/min, and the time is 4-5 h.
Optionally, the mass ratio of the ball material of the ball mill may be 60: 1. 70: 1. 80: 1. 90:1 or (60-90): 1, the rotation speed can be 500r/min, 550r/min, 600r/min, 650r/min or 500-650r/min, and the time can be 4h, 4.5h, 5h or 4-5 h.
In an alternative embodiment, the drying temperature is 100-120 ℃ and the drying time is 4-5 h.
Optionally, the drying temperature can be any value between 100 ℃, 110 ℃, 120 ℃ or 100-120 ℃, and the drying time can be any value between 4h, 4.5h, 5h or 4-5 h.
In an alternative embodiment, the presintering atmosphere is air;
in an alternative embodiment, the temperature raising procedure of the pre-sintering is as follows: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min at 100-500 ℃, the heating rate is 1-2 ℃/min at 400-500 ℃, the temperature of the heating end point is 500-550 ℃, and the sintering time is 5-7 h.
Optionally, in the pre-sintering temperature rise procedure: the heating rate before 100 ℃ can be any value between 1 ℃/min, 1.5 ℃/min, 2 ℃/min or 1-2 ℃/min, the heating rate between 100 ℃ and 500 ℃ can be any value between 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min or 2-5 ℃/min, the heating rate between 400 ℃ and 500 ℃ can be any value between 1 ℃/min, 1.5 ℃/min, 2 ℃/min or 1-2 ℃/min, the temperature-rise end point temperature can be any value between 500 ℃, 510 ℃, 520 ℃, 530 ℃, 540 ℃, 550 ℃ or 500-.
In an alternative embodiment, the temperature raising procedure of the secondary sintering is as follows: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min between 100 ℃ and 850 ℃, the heating rate is 1-2 ℃/min between 850 ℃ and 950 ℃, the temperature of the heating end point is 900-.
Optionally, in the temperature raising procedure of the secondary sintering: the heating rate before 100 ℃ can be any value between 1 ℃/min, 1.5 ℃/min, 2 ℃/min or 1-2 ℃/min, the heating rate between 100 ℃ and 850 ℃ can be any value between 2 ℃/min, 3 ℃/min, 4 ℃/min, 5 ℃/min or 2-5 ℃/min, the heating rate between 850 ℃ and 950 ℃ can be any value between 1 ℃/min, 1.5 ℃/min, 2 ℃/min or 1-2 ℃/min, the temperature of the heating end point can be any value between 900 ℃, 910 ℃, 920 ℃, 930 ℃, 940 ℃, 950 ℃, 960 ℃, 970 ℃, 980 ℃, 990 ℃, 1000 ℃ or 900-1000 ℃, and the sintering time can be any value between 10h, 11h, 12h or 10-12 h.
In an alternative embodiment, the secondary sintering is followed by pulverization and separation;
in an alternative embodiment, the screen used for the separation is 200 mesh, and the undersize is taken.
The application also provides a lithium ion battery anode, and the raw material of the lithium ion battery anode comprises the Ti-Cr co-doped high-voltage spinel anode material.
The application also provides a lithium ion battery, which comprises the lithium ion battery anode.
Embodiments of the present application will be described in detail below with reference to specific examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present application and should not be construed as limiting the scope of the present application. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The nickel source used in the examples of the present application is nickel oxide (AR) and the titanium source is titanium dioxide (TiO) 2 Not less than 99%), the chromium source is chromic oxide (AR), and the chromium source is purchased from Shanghai Allantin Biotech Co., Ltd; the manganese source is manganese monoxide (MnO 99%) and is purchased from Shanghai Michelin Biotechnology, Inc.; the lithium source being Li 2 CO 3 (AR) available from Szegaku corporation.
Example 1
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.47:0.05:0.03 in an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of isopropanol into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the blast drying box is 100-120 ℃, and the drying time is 4-5 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 500 ℃ is 5 ℃/min, the temperature rise rate between 400 ℃ and 500 ℃ is 2 ℃/min, the temperature rise end point temperature is 550 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate of 100-850 ℃ is 5 ℃/min, the temperature rise rate of 850-950 ℃ is 2 ℃/min, the temperature rise end point is 950 ℃, and the sintering time is 10 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.47 Cr 0.03 O 4 。
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V.
The button half cell manufacturing and performance testing method is as follows:
1. material drying (vacuum oven 110 degree drying 12 hours)
2. Weighing the ingredients (material: conductive agent: binder):
the material is conductive agent binder (LNMO: conductive carbon: binder) 90:5:5, and the solid content in the binder is 0.1g (binder with PVDF: NMP 1:9, wherein the PVDF content accounts for 10%).
3. Mixed material (material: conductive agent: binder) + NMP:
step (1): pouring the weighed powder material and the conductive agent into a centrifugal tank, and mixing for 1 time;
step (2): adding a binder and a proper amount of NMP, and mixing for 2 times; mixing centrifuge parameters (Step1: revolution 960 time 150s, Step2: revolution 1280 time 120s, Step3: revolution 1460 time 90 s).
4. Coating preparation:
step (1): transferring the slurry transferred by the mixer into a coating machine for coating operation;
step (2): putting the coated aluminum foil into a vacuum oven (110 ℃) for 2 hours;
and (3): compacting the dried aluminum foil by using a roller press;
and (4): the rolled aluminum foil was placed in a vacuum oven (110 ℃ C.) for 12 hours.
5. Manufacturing a battery;
step (1): cutting the rolled and dried pole piece by a sheet cutter to obtain a phi 14mm wafer;
step (2): weighing the cut pole piece by using a balance, and making a corresponding record;
and (3): continuously putting the pole piece into a vacuum oven to be dried (110 ℃) for 3 hours;
and (4): and putting the pole piece into a glove box for assembly, and assembling the battery. (the amount of the electrolyte is slightly adjusted according to the active quality of the pole piece);
and (5): and sealing the assembled battery by using a sealing machine.
6. And (3) testing the battery performance:
the battery capacity, cycle and rate performance are tested by Shenzhen New Wille electronics Limited (CT-4000).
The first-circle discharge capacity is 112.31mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 31.02% after 300 cycles at the test temperature of 60 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the specific discharge capacity is respectively 105.42mAh/g, 105.78mAh/g, 111.24mAh/g, 106.13mAh/g, 99.76Ah/g, 81.28mAh/g, 52.34mAh/g and 104.92 mAh/g.
Example 2
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.47:0.05:0.03 in an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of polyvinylpyrrolidone into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the heating rate before 100 ℃ is 2 ℃/min, the heating rate at 100-500 ℃ is 5 ℃/min, the heating rate at 400-500 ℃ is 2 ℃/min, the temperature-rise end point temperature is 550 ℃, and the sintering time is 7 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 850 ℃ is 5 ℃/min, the temperature rise rate between 850 ℃ and 950 ℃ is 2 ℃/min, the temperature rise end point temperature is 950 ℃, and the sintering time is 10 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.47 Cr 0.03 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. The first-circle discharge capacity is 113.46mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 34.28 percent at 1C and the testing temperature of 60 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 106.08mAh/g, 106.66mAh/g, 108.24mAh/g, 106.99mAh/g, 101.24Ah/g, 83.72mAh/g, 54.51mAh/g and 105.39mAh/g respectively.
Example 3
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.45:0.05:0.05 by using an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of isopropanol into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 500 ℃ is 5 ℃/min, the temperature rise rate between 400 ℃ and 500 ℃ is 2 ℃/min, the temperature rise end point temperature is 500 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace for secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate of 100-850 ℃ is 5 ℃/min, the temperature rise rate of 850-950 ℃ is 2 ℃/min, and the temperature rise is finishedThe point temperature is 950 ℃, and the sintering time is 10 hours; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.45 Cr 0.05 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. The first-circle discharge capacity is 116.45mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 78.92% after 300 cycles at the test temperature of 60 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 114.31mAh/g, 114.24mAh/g, 115.62mAh/g, 114.81mAh/g, 111.27Ah/g, 105.08mAh/g, 94.16mAh/g and 105.57mAh/g respectively.
Example 4
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.45:0.05:0.05 by using an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of polyvinylpyrrolidone into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 500 ℃ is 5 ℃/min, the temperature rise rate between 400 ℃ and 500 ℃ is 2 ℃/min, the temperature rise end point temperature is 550 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 850 ℃ is 5 ℃/min, the temperature rise rate between 850 ℃ and 950 ℃ is 2 ℃/min, the temperature rise end point temperature is 950 ℃, and the sintering time is 10 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.45 Cr 0.05 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. The first-circle discharge capacity is 118.46mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 92.06% after 300 cycles at the test temperature of 60 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 116.23mAh/g, 118.24mAh/g, 119.35mAh/g, 117.92mAh/g, 114.72Ah/g, 107.15mAh/g, 97.83mAh/g and 118.90mAh/g respectively.
Example 5
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.43:0.05:0.07 by using an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of isopropanol into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the heating rate before 100 ℃ is 2 ℃/min, the heating rate at 100-500 ℃ is 5 ℃/min, the heating rate at 400-500 ℃ is 2 ℃/min, the temperature-rise end point temperature is 550 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 850 ℃ is 5 ℃/min, the temperature rise rate between 850 ℃ and 950 ℃ is 2 ℃/min, the temperature rise end point temperature is 950 ℃, and the sintering time is 12 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.43 Cr 0.07 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. The first-circle discharge capacity is 115.91mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 70.88% after 300 cycles at the test temperature of 60 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 113.74mAh/g, 113.21mAh/g, 112.02mAh/g, 111.57mAh/g, 110.66Ah/g, 102.73mAh/g, 91.24mAh/g and 104.30mAh/g respectively.
Example 6
The embodiment provides a Ti-Cr co-doped high-voltage spinel cathode material, and the preparation method comprises the following steps:
(1) grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.43:0.05:0.07 by using an agate grinding pot, adding the ground materials into an agate grinding pot filled with absolute ethyl alcohol, dissolving the materials to obtain a mixed suspension, and adding 1 wt% of polyvinylpyrrolidone into the suspension; the addition amount of the absolute ethyl alcohol is preferably that the absolute ethyl alcohol is completely soaked in the material;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 500 ℃ is 5 ℃/min, the temperature rise rate between 400 ℃ and 500 ℃ is 2 ℃/min, the temperature rise end point temperature is 550 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 850 ℃ is 5 ℃/min, the temperature rise rate between 850 ℃ and 950 ℃ is 2 ℃/min, the temperature rise end point temperature is 950 ℃, and the sintering time is 112 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.43 Cr 0.07 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. The first-circle discharge capacity is 114.71mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 68.76% after 300 cycles at the test temperature of 60 ℃ at 1C. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured specific discharge capacities are 113.23mAh/g, 114.02mAh/g, 115.72mAh/g, 113.08mAh/g, 109.42Ah/g, 101.56mAh/g, 88.46mAh/g and 101.60mAh/g respectively.
Comparative example 1
The procedure described in example 1 was followed for LiNi only 0.5 Mn 1.5 O 4 (no doping) was performed to prepare and test electrochemical properties. The first-circle discharge capacity is 111.23mAh/g under the test temperature of 30 ℃ and 0.2 ℃; the capacity retention rate is 29.87 percent at 1C and the testing temperature of 30 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 108.02mAh/g, 112.48mAh/g, 110.63mAh/g, 105.28mAh/g, 98.87mAh/g, 79.56mAh/g, 47.36mAh/g and 113.72mAh/g respectively.
Comparative example 2
(1) Grinding a lithium source, a nickel source, a manganese source, a titanium source and a chromium source in a molar ratio of 1:0.45:1.43:0.05:0.07 by using an agate grinding pot, and then adding the materials into an agate grinding tank filled with absolute ethyl alcohol for dissolving to obtain a mixed suspension;
(2) ball-milling the mixed suspension obtained in the step (1) to obtain slurry; the equipment used for ball milling is a planetary ball mill, the medium is agate beads, the ball-material ratio is 90:1, the ball milling rotating speed is 500r/min, and the ball milling time is 4 hours;
(3) placing the slurry obtained in the step (2) in a forced air drying oven, and drying to obtain solid powder; the working temperature of the air-blast drying oven is 120 ℃, and the drying time is 4 hours;
(4) putting the solid powder obtained in the step (3) into a porcelain boat, transferring the porcelain boat into a muffle furnace, and presintering in the atmosphere of air to obtain precursor powder of the Ti-Cr element co-doped high-pressure spinel cathode material; the pre-sintering temperature is 500 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 500 ℃ is 5 ℃/min, the temperature rise rate between 400 ℃ and 500 ℃ is 2 ℃/min, the temperature rise end point temperature is 550 ℃, and the sintering time is 5 h;
(5) grinding the precursor powder of the high-pressure spinel cathode material obtained in the step (4) in an agate grinding bowl, then loading the ground precursor powder into a porcelain boat, transferring the porcelain boat into a muffle furnace, and performing secondary sintering, wherein the sintering atmosphere is air, the secondary sintering temperature is 950 ℃, the temperature rise rate before 100 ℃ is 2 ℃/min, the temperature rise rate between 100 ℃ and 850 ℃ is 5 ℃/min, the temperature rise rate between 850 ℃ and 950 ℃ is 2 ℃/min, the temperature rise end point temperature is 950 ℃, and the sintering time is 12 h; grinding the material obtained after secondary sintering, and sieving the material with a 200-mesh sieve to obtain the Ti-Cr element co-doped high-voltage spinel cathode material with the chemical formula of LiNi 0.45 Ti 0.05 Mn 1.47 Cr 0.03 O 4 ；
The obtained Ti-Cr element co-doped high-voltage spinel cathode material is assembled into a button cell (CR2035) by using a button half cell manufacturing method, and the charge-discharge voltage range is 3.2-4.95V. At 0.2C and the test temperature of 30 ℃, the discharge capacity of the first circle is 114.53 mAh/g; the capacity retention rate is 42.67 percent at 1C and the testing temperature of 60 ℃ after 300 cycles. Under different multiplying powers of 0.1C, 0.2C, 0.5C, 1C, 2C, 5C, 10C and 0.1C and at a test temperature of 60 ℃, the measured discharge specific capacities are 112.99mAh/g, 117.77mAh/g, 115.71mAh/g, 113.20mAh/g, 109.58Ah/g, 100.54mAh/g, 86.51mAh/g and 104.84mAh/g respectively.
The first-turn charge and discharge curves of example 3, comparative example 1 and comparative example 2 at 30 ℃ and 0.2C are shown in FIG. 1; the 300-cycle performance curves of example 3 and comparative examples 1 and 2 at 30 ℃ and 1C are shown in FIG. 2; the cycle performance curves of example 3 and comparative examples 1 and 2 at different magnifications at 60 ℃ are shown in FIG. 3; an SEM image of the Ti — Cr element co-doped high voltage spinel cathode material obtained in example 3 is shown in fig. 4.
The first circle of charge-discharge curve graph shows that the material modified by doping Ti-Cr element and dispersed by 1 wt% isopropanol has higher specific discharge capacity, and the capacity improvement can be attributed to the widening of the lithium ion diffusion channel after the Ti-Cr co-doping and the reduction of the agglomeration of the material in the synthesis process by 1 wt% isopropanol; after 300-circle cycle test, the capacity retention rate of the material subjected to Ti-Cr element doping modification and 1 wt% isopropanol dispersion treatment is highest, because strong bond energy of Ti-O bonds and Cr-O bonds improves the structural stability of the material, and meanwhile, the dispersion effect of 1 wt% isopropanol also avoids the occurrence of large particle agglomeration, so that the cycle performance of the material is improved; the room temperature rate performance test result also shows that the material modified by doping Ti-Cr element and subjected to 1 wt% isopropanol dispersion treatment has more excellent high rate discharge performance, returns to 0.1C for discharge after 10C high rate discharge, still returns to 0.1C for initial discharge capacity test, and also shows excellent reversible performance of the material; as can be seen from the SEM image, the synthesized material is a typical spinel polyhedral structure.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solutions of the present application, and not to limit the same; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present application.
Moreover, those of skill in the art will understand that although some embodiments herein include some features included in other embodiments, not others, combinations of features of different embodiments are meant to be within the scope of the application and form different embodiments. For example, in the claims above, any of the claimed embodiments may be used in any combination. The information disclosed in this background section is only for enhancement of understanding of the general background of the application and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.

Claims (10)

1. A Ti-Cr co-doped high-voltage spinel cathode material is characterized in that the chemical formula is LiNi 0.5-x Mn 1.5- y Ti x Cr y O 4 Wherein x is more than or equal to 0.001 and less than or equal to 0.06, and y is more than or equal to 0.001 and less than or equal to 0.07.
2. The method for preparing the Ti-Cr co-doped high-voltage spinel cathode material according to claim 1, comprising:
mixing raw materials including a lithium source, a nickel source, a manganese source, a titanium source, a chromium source, a solvent and a dispersant to obtain slurry;
drying the slurry to obtain solid powder, and then pre-sintering the solid powder to obtain a precursor;
and carrying out secondary sintering on the precursor to obtain the Ti-Cr co-doped high-voltage spinel cathode material.
3. The method of claim 2, wherein the lithium source comprises one or more of lithium carbonate, lithium acetate, lithium nitrate;
the nickel source comprises nickel oxide and/or nickel acetate tetrahydrate;
the manganese source comprises one or more of manganese oxide, manganese dioxide and mangano-manganic oxide;
the titanium source comprises titanium monoxide and/or titanium dioxide;
the chromium source comprises chromium dioxide and/or chromium sesquioxide;
the solvent comprises absolute ethyl alcohol;
the dispersant comprises isopropanol and/or polyvinylpyrrolidone, and the dosage of the dispersant is 1 wt% of the slurry.
4. The method of claim 2, wherein the mixing further comprises ball milling;
the ball-milling ball material mass ratio is (60-90): 1, the rotating speed is 500-650r/min, and the time is 4-5 h.
5. The method as claimed in claim 2, wherein the drying temperature is 100 ℃ and 120 ℃ and the drying time is 4-5 h.
6. The method according to claim 2, wherein the atmosphere of the pre-sintering is air;
the temperature rising procedure of the pre-sintering is as follows: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min at 100-500 ℃, the heating rate is 1-2 ℃/min at 400-500 ℃, the temperature-rising end point temperature is 500-.
7. The preparation method according to claim 2, wherein the temperature rise procedure of the secondary sintering is: the heating rate is 1-2 ℃/min before 100 ℃, the heating rate is 2-5 ℃/min between 100 ℃ and 850 ℃, the heating rate is 1-2 ℃/min between 850 ℃ and 950 ℃, the temperature of the heating end point is 900-.
8. The production method according to any one of claims 2 to 7, characterized by further comprising, after the secondary sintering, pulverization and separation;
the screen mesh used for separation is 200 meshes, and undersize materials are taken.
9. A positive electrode for a lithium ion battery, characterized in that its raw material comprises the Ti-Cr co-doped high-voltage spinel positive electrode material according to claim 1.
10. A lithium ion battery comprising the lithium ion battery positive electrode according to claim 9.
CN202210758193.1A 2022-06-29 2022-06-29 Ti-Cr co-doped high-voltage spinel cathode material, preparation method thereof, lithium ion battery cathode and lithium ion battery Pending CN114975985A (en)

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