CN110911663A - Lithium-rich manganese-based composite lithium battery positive electrode material and manufacturing method thereof - Google Patents
Lithium-rich manganese-based composite lithium battery positive electrode material and manufacturing method thereof Download PDFInfo
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Abstract
The invention provides a lithium-rich manganese-based composite lithium battery positive electrode material and a preparation method thereof, wherein the lithium-rich manganese-based composite lithium battery positive electrode material comprises the following raw materials: molecular formula of xLi2MnO3·(1‑x)LiMO2The lithium-rich manganese-based composite lithium battery positive electrode material has the advantages of high specific capacity, first cycle voltage of about 4.7V, stable high-temperature cycle performance and the like, and the process is simpleThe method has the advantages of low equipment strength requirement, short production period, suitability for industrial production, and great economic value and practical value.
Description
Technical Field
The invention relates to the technical field of lithium battery material preparation, in particular to a lithium-rich manganese-based composite lithium battery positive electrode material and a manufacturing method thereof.
Background
In order to meet the requirements of the power battery marketThe energy density of the lithium battery needs to be improved, the future trend is mainly towards the development of high specific energy and high discharge voltage, and more spinel LiMn is researched in manganese-based positive electrode materials2O4Layered LiMnO2And a layered solid solution positive electrode material, wherein layered LiMnO2The stability of the structure is poor during charging and discharging, and the research is not much at present. Spinel LiMn2O4 can function in two voltage ranges, 4V and 3V. For the 4V region, the lithium ion intercalation and deintercalation at the tetrahedral 8a position of the spinel structure are involved; for the 3V region, there is a correlation between the intercalation and deintercalation of lithium ions at the octahedral 16c sites of the spinel structure. The intercalation and deintercalation of lithium ions at the tetrahedral sites of the spinel structure does not cause significant changes in the structure of the sample. However, when the charging and discharging depth is too large, due to the John-Teller distortion effect of lithium ions, the insertion and extraction of lithium ions in an octahedron can cause the sample structure to change from cubic to tetragonal, the discharge capacity is rapidly attenuated, along with the development of science and technology, the lithium battery industry also faces challenges and opportunities, how to achieve the best and the best performance of the power battery material becomes a popular problem in the current lithium battery industry, and although the current performance of the lithium-rich manganese positive electrode material serving as the positive electrode material of the power battery is greatly improved, the cycle performance, the rate capability and the safety of the lithium-rich manganese positive electrode material are further improved.
Disclosure of Invention
Aiming at the problems, the invention provides the composite lithium battery diaphragm which is good in tensile strength and high in liquid absorption rate of electrolyte and the preparation method thereof.
The technical scheme adopted by the invention for solving the problems is as follows:
the invention provides a lithium-rich manganese-based composite lithium battery positive electrode material which comprises the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO25-100 parts of lithium-rich manganese anode base material,
1-10 parts of nano diamond alkene,
1-15 parts of silicon dioxide,
2-5 parts of ferric oxide,
1-50 parts of ethylene glycol,
1-2 parts of solid paraffin,
0.5-2 parts of rare earth oxide.
M is one or more of Ni, Co, Al, Cr, Au and Mg, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
Furthermore, the rare earth samarium compound is one of samarium oxide, samarium carbonate and samarium nitrate, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2Weighing compounds of a lithium source, a manganese source and M according to the stoichiometric ratio, mixing, adding ethylene glycol, stirring, wet-grinding, and uniformly mixing to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
Further, the sintering temperature in the step (3) is 500-.
Further, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a Proportion tableThe area is 8.2-12.5 m2/g。
Further, applying pressure of 20-100 MPa to the copper-chromium mixed powder in the step (5), and continuing the whole sintering process; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
The invention has the beneficial effects that:
the lithium-rich manganese-based composite lithium battery positive electrode material provided by the invention has the advantages of high specific capacity (up to about 300mAh/g), first cycle voltage up to about 4.7V, stable high-temperature cycle performance and the like.
Detailed Description
FIG. 1 is an XRD (X-ray diffraction) pattern of an example 1 of the lithium-rich manganese-based composite lithium battery cathode material;
FIG. 2 is an SEM image of the positive electrode material of the lithium-rich manganese-based composite lithium battery of example 1;
fig. 3 is a cycle characteristic curve of the positive electrode material example 1 of the lithium-rich manganese-based composite lithium battery of the present invention.
Detailed Description
The following embodiments are specifically illustrated by the following examples, which are given for the purpose of illustration only and are not to be construed as limiting the invention, for reference and illustration only, and are not to be construed as limiting the scope of the invention, since many variations of the invention can be made without departing from the spirit and scope thereof.
Example 1
The embodiment provides a lithium-rich manganese-based composite lithium battery cathode material, which comprises the following raw materials: molecular formula xLi2MnO3·(1-x)LiMO250 parts of the lithium-rich manganese anode base material,
5 parts of nano diamond alkene,
7 parts of silicon dioxide,
3 parts of ferric oxide,
25 portions of ethylene glycol,
1 part of solid paraffin,
0.5 part of rare earth oxide.
M is Ni, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
In the embodiment, the rare earth samarium compound is samarium oxide, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2Weighing a lithium source, a manganese source and a compound (nickel oxide) of M according to the stoichiometric ratio, mixing, adding ethylene glycol, stirring, wet-grinding, and uniformly mixing to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
In this embodiment, the sintering temperature in step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
In the embodiment, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
In the embodiment, the step (5) applies a pressure of 20-100 MPa to the copper-chromium mixed powder, and the whole sintering process is continued; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
Example 2
The embodiment provides a lithium-rich manganese-based composite lithium battery cathode material, which comprises the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO 250 parts of the lithium-rich manganese anode base material,
5 parts of nano diamond alkene,
7 parts of silicon dioxide,
3 parts of ferric oxide,
25 portions of ethylene glycol,
1 part of solid paraffin,
0.5 part of rare earth oxide.
M is Co, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
In the embodiment, the rare earth samarium compound is samarium oxide, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2The components of (A) are stoichiometrically weighed lithium source, manganese source and M compound (CoCO)3) Mixing, adding ethylene glycol, stirring, wet grinding, and mixing uniformly to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
In this embodiment, the sintering temperature in step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
In the embodiment, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
In the embodiment, the step (5) applies a pressure of 20-100 MPa to the copper-chromium mixed powder, and the whole sintering process is continued; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
Example 3
The embodiment provides a lithium-rich manganese-based composite lithium battery cathode material, which comprises the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO 250 parts of the lithium-rich manganese anode base material,
5 parts of nano diamond alkene,
7 parts of silicon dioxide,
3 parts of ferric oxide,
25 portions of ethylene glycol,
1 part of solid paraffin,
0.5 part of rare earth oxide.
M is Cr, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
In the embodiment, the rare earth samarium compound is samarium oxide, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2The components of (A) are stoichiometrically weighed lithium source, manganese source and M compound (CrO)3) Mixing, adding ethylene glycol, stirring, wet grinding, and mixing uniformly to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
In this embodiment, the sintering temperature in step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
In the embodiment, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
In the embodiment, the step (5) applies a pressure of 20-100 MPa to the copper-chromium mixed powder, and the whole sintering process is continued; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
Example 4
The present embodiment provides aThe lithium-rich manganese-based composite lithium battery positive electrode material comprises the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO 250 parts of the lithium-rich manganese anode base material,
5 parts of nano diamond alkene,
7 parts of silicon dioxide,
3 parts of ferric oxide,
25 portions of ethylene glycol,
1 part of solid paraffin,
0.5 part of rare earth oxide.
M is Au, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
In the embodiment, the rare earth samarium compound is samarium oxide, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2The components of (A) are stoichiometrically weighed lithium source, manganese source and M compound (Au)2O3) Mixing, adding ethylene glycol, stirring, wet grinding, and mixing uniformly to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
In this embodiment, the sintering temperature in step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
In the embodiment, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
In the embodiment, the step (5) applies a pressure of 20-100 MPa to the copper-chromium mixed powder, and the whole sintering process is continued; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
Example 5
The embodiment provides a lithium-rich manganese-based composite lithium battery cathode material, which comprises the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO 250 parts of the lithium-rich manganese anode base material,
5 parts of nano diamond alkene,
7 parts of silicon dioxide,
3 parts of ferric oxide,
25 portions of ethylene glycol,
1 part of solid paraffin,
0.5 part of rare earth oxide.
M is Mg, and x is more than or equal to 0.3 and less than or equal to 0.6.
The nano diamond alkene improves the mechanical, thermal and electrical properties of the polymer material, and can improve the ionic conductivity and the charge-discharge cycle performance.
In the embodiment, the rare earth samarium compound is samarium oxide, and the addition of the rare earth element can effectively improve the charge-discharge capacity of the anode material and improve the electrochemical performance of the material.
A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material comprises the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2The components of (A) are stoichiometrically weighed lithium source, manganese source and M compound (MgCO)3) Mixing, adding ethylene glycol, wet grinding while stirring, and mixingForming a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
In this embodiment, the sintering temperature in step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
In the embodiment, the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
In the embodiment, the step (5) applies a pressure of 20-100 MPa to the copper-chromium mixed powder, and the whole sintering process is continued; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
And (3) performance testing:
the results of the tests performed on examples 1 to 5 are shown in the following table:
| examples | Specific discharge capacity (mAh/g) | Tap density (g/cm)3) |
| Example 1 | 300.1 | 1.21 |
| Example 2 | 284.1 | 1.17 |
| Example 3 | 286.7 | 1.08 |
| Example 4 | 275.6 | 1.02 |
| Example 5 | 279.8 | 1.13 |
The specific discharge capacity is measured under the conditions of 2.0-4.7V and 0.1C multiplying power.
When XRD, SEM and cycle characteristic tests are carried out on example 1, the main phase is rich in lithium and manganese, the crystallinity is high, the crystal grains are uniform, the cycle performance is stable, and the results are shown in figures 1-3.
The lithium-rich manganese-based composite lithium battery positive electrode material provided by the invention has the characteristics of high liquid absorption rate, good thermal shrinkage rate, and excellent conductivity and charge-discharge cycle performance, the nano diamond alkene improves the mechanical, thermal and electrical properties of a polymer material, and simultaneously can improve the liquid absorption rate, the thermal shrinkage rate, the ionic conductivity and the charge-discharge cycle performance of a diaphragm, and the nano silicon carbide whisker are used for improving the high-temperature-resistant shrinkage performance and the tensile strength of the power lithium-rich manganese-based composite lithium battery positive electrode material.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (6)
1. The lithium-rich manganese-based composite lithium battery cathode material is characterized by comprising the following raw materials: molecular formula of xLi2MnO3·(1-x)LiMO25-100 parts of lithium-rich manganese anode base material,
1-10 parts of nano diamond alkene,
1-15 parts of silicon dioxide,
2-5 parts of ferric oxide,
1-50 parts of ethylene glycol,
1-2 parts of solid paraffin,
0.5-2 parts of rare earth oxide.
M is one or more of Ni, Co, Al, Cr, Au and Mg, and x is more than or equal to 0.3 and less than or equal to 0.6.
2. The lithium-rich manganese-based composite lithium battery positive electrode material as claimed in claim 1, wherein: the rare earth samarium compound is one of samarium oxide, samarium carbonate and samarium nitrate.
3. A preparation method of a lithium-rich manganese-based composite lithium battery positive electrode material is characterized by comprising the following steps:
(1) according to the formula xLi2MnO3·(1-x)LiMO2Weighing compounds of a lithium source, a manganese source and M according to the stoichiometric ratio, mixing, adding ethylene glycol, stirring, wet-grinding, and uniformly mixing to form a mixed material;
(2) adding silicon dioxide, ferric oxide, solid paraffin and rare earth oxide into the mixed material, adding ethylene glycol again for secondary stirring, and grinding to form an initial raw material;
(3) sintering, crushing and sieving the obtained initial raw materials to form mixed powder;
(4) mixing and stirring the mixed powder and nano diamond alkene, and adding a stearamide dispersant and an ethanol solvent for wet grinding to form a target mixture;
(5) and (3) loading the obtained target mixture into a graphite mold, and then placing the graphite mold into a discharge plasma sintering furnace for low-temperature rapid sintering, crushing and sieving to obtain a target product.
4. The preparation method of the lithium-rich manganese-based composite lithium battery positive electrode material according to claim 3, characterized in that: the sintering temperature in the step (3) is 500-700 ℃, and the sintering time is 0.5-2 h.
5. The preparation method of the lithium-rich manganese-based composite lithium battery positive electrode material according to claim 3, characterized in that: the average particle size distribution D50 of the target product in the step (5) is 1-10 μm; the tap density is 1 to 1.8g/cm3(ii) a The specific surface area is 8.2-12.5 m2/g。
6. The preparation method of the lithium-rich manganese-based composite lithium battery positive electrode material according to claim 3, characterized in that: step (5) applying pressure of 20-100 MPa to the copper-chromium mixed powder, and continuing the whole sintering process; the vacuum degree is 10 < -1 > to 10 < -3 > Pa; the sintering temperature is 800-900 ℃, the heating rate is 50-300 ℃/min, and the heat preservation time is 1-5 min.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN113745462A (en) * | 2021-09-08 | 2021-12-03 | 四川朗晟新能源科技有限公司 | Lithium battery positive electrode material and preparation method thereof |
| CN116344791A (en) * | 2023-05-26 | 2023-06-27 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
-
2019
- 2019-11-13 CN CN201911107551.7A patent/CN110911663A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111509224A (en) * | 2020-04-17 | 2020-08-07 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN111509224B (en) * | 2020-04-17 | 2021-07-23 | 中南大学 | Linked modified lithium-rich manganese-based cathode material and preparation method thereof |
| CN113745462A (en) * | 2021-09-08 | 2021-12-03 | 四川朗晟新能源科技有限公司 | Lithium battery positive electrode material and preparation method thereof |
| CN116344791A (en) * | 2023-05-26 | 2023-06-27 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
| CN116344791B (en) * | 2023-05-26 | 2023-08-08 | 天津巴莫科技有限责任公司 | Positive electrode material, preparation method thereof, positive electrode plate and battery |
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