CN116282231A - Preparation method of layered-spinel composite phase positive electrode material - Google Patents
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 38
- 239000011029 spinel Substances 0.000 title claims abstract description 38
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- 239000007774 positive electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 230000007935 neutral effect Effects 0.000 claims description 7
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- 238000011282 treatment Methods 0.000 description 4
- 229910008514 Li1.2Mn0.54Ni0.13Co0.13O2 Inorganic materials 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
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- 239000002253 acid Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
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- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
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- 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
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- C01G53/50—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [MnO2]n-, e.g. Li(NixMn1-x)O2, Li(MyNixMn1-x-y)O2
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Abstract
The invention discloses a preparation method of a layered-spinel composite phase positive electrode material, which has a molecular formula of a [ xLi ] 2 MnO 3 ·(1‑x)LiMO 2 ]·(1‑a)LiMn 2‑y N y O 4 Wherein 0 < x < 1,0 < a < 1,0 < y < 1, specifically comprising the following steps: (1) By Li 2 MnO 3 Based oxide as precursor, li 2 MnO 3 Dispersing the basic oxide, the soluble M salt and the soluble N salt in a non-acidic solution, fully and uniformly mixing, and drying to obtain mixed powder; (2) And roasting the mixed powder to obtain the layered-spinel composite phase anode material. The invention does not need a complex ion exchange process under an acidic condition, uses Li 2 MnO 3 The base oxide is a precursor, and in a non-acidic solution, the base oxide is prepared by simply mixing and then drying and roasting, and has excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a preparation method of a layered-spinel composite phase positive electrode material.
Background
Along with the rapid increase of world economy, the demands of various countries on energy are continuously increased, the traditional fossil energy is accelerating and attenuating and even is exhausted, and clean energy such as solar energy, wind energy and the like is widely developed and utilized, but the uncertainty and intermittence of the traditional fossil energy prevent the traditional fossil energy from being popularized and applied on a large scale. With the development of renewable energy technology, new energy storage devices represented by lithium ion batteries are receiving high attention. The lithium ion battery has the characteristics of high energy density, high voltage platform, good cycle performance, multiplying power performance and the like, is widely applied to the aspects of mobile communication tools, electric tools, energy storage equipment and the like at present, and is also widely used as a material in the aerospace field and the military industry field. Among the key materials of lithium ions, the positive electrode material directly affects the cycle stability, energy density and production cost of the battery.
In view of urgent demands for energy, large-scale popularization and use, safety and other problems, manganese oxide cathode materials using Mn as a transition metal are favored. Wherein the layered cathode material xLi 2 MnO 3 ·(1-x)LiMO 2 The (M=Mn, ni, co and other transition metal elements) has high specific discharge capacity of more than or equal to 250mAh/g, good thermal stability and lower cost. However, the layered cathode material still has problems of poor rate capability, low initial coulombic efficiency, serious capacity fade, and the like. To improve electrochemical stability of the battery, a layered-spinel composite phase cathode material (a [ xLi 2 MnO 3 ·(1-x)LiMO 2 ]·(1-a)LiNi 0.5 Mn 1.5 O 4 ). Compared with the layered anode material, the spinel phase composite is introduced to effectively improve the problems of capacity, voltage attenuation and the like of the electrode material in the circulation process.
The complexity of the layered cathode material structure is mainly due to the difference of the preparation methods. The common preparation methods mainly comprise two methods, namely, uniformly mixing raw materials, and synthesizing the raw materials through high-temperature sintering to obtain materials, such as a sol-gel method, a solid-phase method and the like; and secondly, preparing an oxide precursor, and then lithiating at a high temperature to obtain a target product, such as a coprecipitation method, a hydrothermal method and the like. The preparation method can obtain target products, but has defects, such as coprecipitation method can control the precipitation of main elements such as Ni, mn and the like, but cannot control the uniform precipitation of other doping elements; the solid phase method is not easy to control the granularity and the obtained product has insufficient performance; the sol-gel method has high cost and is difficult to popularize and apply on a large scale; the hydrothermal method is difficult to produce in large scale.
Thackeray et al in Li 2 MnO 3 The material is used as a precursor, and is put into a nitric acid solution to pass through H + /Li + Exchange, and then add other metal cations (M n+ ) Realizing M through high temperature treatment n+ And H is + Exchange of Li with 2 MnO 3 And partially converting to form a layered lithium-rich manganese-based positive electrode material or a spinel-phase positive electrode material. The ion exchange synthesis method can select various metal cations to realize controllable composition, but has the following problems: firstly, nitric acid is adopted, the post-treatment process is complex, and environmental pollution and great safety risks exist; secondly, ion exchange treatment is needed to be carried out in acid liquor, uncontrollability exists in the ion exchange process, and the large-scale industrialization is difficult to realize.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a preparation method of a moderate and simple-process layered-spinel composite phase positive electrode material which can be scaled up without a complex ion exchange process under an acidic condition, and uses Li 2 MnO 3 The base oxide is a precursor, in a non-acidic solution (or medium), by simple means onlyMixing, drying and roasting to obtain the layered-spinel composite phase anode material with excellent electrochemical performance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a preparation method of a layered-spinel composite phase positive electrode material, wherein the molecular formula of the layered-spinel composite phase positive electrode material is a [ xLi ] 2 MnO 3 ·(1-x)LiMO 2 ]·(1-a)LiMn 2-y N y O 4 Wherein 0 < x < 1,0 < a < 1,0 < y < 1, M is one or more of Mn, ni, co, fe, al, mg, zr, cr, ti, etc.; n is one or more of Ni, co, fe, al, mg, zr, cr, ti and the like; the method specifically comprises the following steps:
(1) By Li 2 MnO 3 Based oxide as precursor, li 2 MnO 3 Dispersing the basic oxide, the soluble M salt and the soluble N salt in a non-acidic solution, fully and uniformly mixing, and drying to obtain mixed powder;
(2) And roasting the mixed powder to obtain the layered-spinel composite phase anode material.
Preferably, the M is one or more of Mn, ni and Co; n is one or more of Ni and Co.
Preferably, in step (1), the Li 2 MnO 3 The base oxide is pure phase Li 2 MnO 3 And Li (lithium) 2 MnO 3 At least one of the doping materials; li (Li) 2 MnO 3 The doping material is Li 2 MnO 3 A material obtained by doping at least one of Li, mn and O sites, for example Li 1.8 Na 0.2 MnO 3 、Li 2 Mn 0.96 Ti 0.04 O 3 、Li 2 MnO 2.98 F 0.02 Etc.
Li in the present invention 2 MnO 3 The base oxide may be prepared by conventional methods, such as a solid phase method, a coprecipitation method, a hydrothermal method, etc., and will not be described herein.
Preferably, in the step (1), the soluble M salt is at least one of volatile salts such as nitrate and acetate of M; the soluble N salt is at least one of nitrate, acetate and other volatile salts of N.
Preferably, in the step (1), the non-acidic solution is at least one of a neutral solution, such as water, ethanol, etc., and an alkaline solution, such as ammonia, etc.; further preferably a neutral solution; still more preferably water.
Preferably, in the step (2), the roasting temperature is 500-950 ℃ and the roasting time is 2-24h.
The invention has the advantages that:
unlike the complex ion exchange process under acidic conditions, the present invention uses Li 2 MnO 3 The base oxide is a precursor, and it is unexpectedly found that the layered-spinel composite phase anode material can be obtained by simply mixing, drying and roasting in a non-acidic solution, and has excellent electrochemical properties. The preparation process provided by the invention is especially in pure water solution, has a milder environment, reduces excessive damage to a material structure, is environment-friendly, and has a good industrial prospect. The layered-spinel composite phase positive electrode material prepared by the invention has excellent electrochemical performance, and improves the capacity and voltage attenuation of the electrode material in the circulation process.
Drawings
FIG. 1 is an XRD pattern of layered-spinel composite phase cathode materials prepared in example 1, example 2, and comparative example 1 according to the present invention;
FIG. 2 is a scanning electron microscope image of the layered-spinel composite phase positive electrode material prepared in example 1, example 2, and comparative example 1 according to the present invention;
fig. 3 is a charge-discharge graph of the layered-spinel composite phase positive electrode materials prepared in example 1, example 2, and comparative example 1 according to the present invention;
FIG. 4 is a graph showing the cycle performance of the layered-spinel composite phase positive electrode materials prepared according to example 1, example 2, and comparative example 1 of the present invention;
FIG. 5 is a graph showing the rate performance of the layered-spinel composite phase positive electrode materials prepared according to example 1, example 2, and comparative example 1 of the present invention;
Detailed Description
The following examples are intended to further illustrate the technical content of the present invention, but do not limit the scope of the claims of the present invention.
Example 1
(1)Li 2 MnO 3 Preparing a precursor: preparing the precursor material by a solid phase method, namely accurately weighing Li according to the stoichiometric ratio 2 CO 3 And Mn of 2 O 3 (Li is 5 percent excessive), ball milling and mixing, and finally calcining for 20 hours in a muffle furnace at 450 ℃ to obtain Li 2 MnO 3 。
(2) Preparation of a layered-spinel composite phase positive electrode material: according to lamellar phase Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 And spinel LiNi 0.5 Mn 1.5 O 4 Accurately weighing Li according to the molar ratio of 0.9:0.1 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O、Ni(NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Placing O in a 100mL beaker, adding 40mL deionized water, magnetically stirring and mixing uniformly, then placing in a 80 ℃ blast drying oven for drying for 12 hours, placing the obtained mixed powder in a corundum crucible, placing in a muffle furnace for calcining for 6 hours at 750 ℃ to finally obtain the layered-spinel composite phase anode material 0.9Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ·0.1LiNi 0.5 Mn 1.5 O 4 The reaction mixture was designated as S-LMNCO.
Example 2
(1)Li 2 MnO 3 Preparing a precursor: preparing the precursor material by a solid phase method, namely accurately weighing Li according to the stoichiometric ratio 2 CO 3 And Mn of 2 O 3 (Li is 5 percent excessive), ball milling and mixing, and finally calcining for 20 hours in a muffle furnace at 450 ℃ to obtain Li 2 MnO 3 。
(2) Preparation of a layered-spinel composite phase positive electrode material: according to lamellar phase Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 And spinel LiNi 0.5 Mn 1.5 O 4 Is accurately called as (1) in the molar ratio of 0.9:0.1Taking Li 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O、Ni(NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 O is placed in a 100mL beaker, 40mL of 25% ammonia water is added, magnetic stirring and mixing are carried out uniformly, then the mixture is placed in a 80 ℃ blast drying box for drying for 12 hours, the obtained mixed powder is placed in a corundum crucible, and is placed in a muffle furnace for calcination for 6 hours at 750 ℃ to finally obtain the layered-spinel composite phase anode material 0.9Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ·0.1LiNi 0.5 Mn 1.5 O 4 And is designated as S-LMNCO-1.
XRD and electrochemical performance tests show that the layered-spinel composite phase anode material can be successfully prepared under the alkaline solution condition, and has excellent electrochemical performance.
Comparative example 1
(1)Li 2 MnO 3 Preparing a precursor: preparing the precursor material by a solid phase method, namely accurately weighing Li according to the stoichiometric ratio 2 CO 3 And Mn of 2 O 3 (Li is 5 percent excessive), ball milling and mixing, and finally calcining for 20 hours in a muffle furnace at 450 ℃ to obtain Li 2 MnO 3 。
(2) Preparation of a layered-spinel composite phase positive electrode material: according to lamellar phase Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 And spinel LiNi 0.5 Mn 1.5 O 4 Accurately weighing Li according to the molar ratio of 0.9:0.1 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O、Ni(NO 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Placing O in a 100mL beaker, adding 40mL of 0.1mol/L nitric acid solution, magnetically stirring and uniformly mixing, then placing in a 80 ℃ blast drying oven for drying for 12 hours, placing the obtained mixed powder in a corundum crucible, placing in a muffle furnace for calcining for 6 hours at 750 ℃, and finally obtaining the layered-spinel composite phase anode material 0.9Li 1.2 Mn 0.54 Ni 0.13 Co 0.13 O 2 ·0.1LiNi 0.5 Mn 1.5 O 4 And is designated as S-LMNCO-2.
XRD testing showed that all samples were typical of lamellar alpha-NaFeO as shown in FIG. 1 2 The structure is that the space group is R3m, and meanwhile, more obvious Li appears between 20 degrees and 25 degrees 2 MnO 3 The superlattice diffraction peak is a characteristic peak of the layered positive electrode material, and the space group is C2/m. XRD characteristic diffraction peaks (311) of the spinel phase (space group Fd-3 m) were found at 36 ° -38 °. Tests show that the layered-spinel composite phase anode material is successfully prepared by adopting the technical method of the invention.
Scanning electron microscopy showed that different solution treatments had less effect on the material morphology as shown in figure 2.
The charge and discharge tests show that in the voltage interval of 2.0-4.8V, as shown in FIG. 3, the charge and discharge processes of all materials show typical charge and discharge curves of the lithium-rich manganese-based positive electrode material, and the inclined area below 4.5V is attributed to Ni 2+ /Ni 4 + And Co 3+ /Co 4+ Long plateau around 4.5V due to Li 2 MnO 3 Electrochemical activation of the components. At the same time, it can be seen that two voltage plateaus occur around about 4.7V, corresponding to spinel material LiNi 0.5 Mn 1.5 O 4 Ni at high voltage 2+ /Ni 3+ /Ni 4+ Is a redox couple of (a). In addition, there is a distinct spinel phase discharge plateau at-2.6V, corresponding to the redox of Mn. The charge-discharge curve further shows that the layered-spinel composite phase anode material is successfully prepared by adopting the technical method.
FIG. 4 is a graph of the cycling performance of the material, showing that the capacity retention of the S-LMNCO at a current density of 1C for 200 cycles is 89%.
FIG. 5 is a graph of the rate capability of the material, with the S-LMNCO still having 146mAhg at a high current density of 10C -1 Is a specific discharge capacity of (a).
The above electrochemical performance test shows that the layered-spinel composite phase positive electrode material with excellent electrochemical performance can be successfully obtained by using the preparation method of the invention. The positive electrode material (S-LMNCO) prepared in the neutral solution has larger discharge specific capacity, good rate capability and better cycle performance than the positive electrode material (S-LMNCO-2) prepared in the acid solution.
Claims (10)
1. A preparation method of a layered-spinel composite phase positive electrode material is characterized by comprising the following steps: the molecular formula of the layered-spinel composite phase positive electrode material is a [ xLi ] 2 MnO 3 ·(1-x)LiMO 2 ]·(1-a)LiMn 2-y N y O 4 Wherein 0 < x < 1,0 < a < 1,0 < y < 1, M is one or more of Mn, ni, co, fe, al, mg, zr, cr, ti; n is one or more than one of Ni, co, fe, al, mg, zr, cr, ti; the method specifically comprises the following steps:
(1) By Li 2 MnO 3 Based oxide as precursor, li 2 MnO 3 Dispersing the basic oxide, the soluble M salt and the soluble N salt in a non-acidic solution, fully and uniformly mixing, and drying to obtain mixed powder;
(2) And roasting the mixed powder to obtain the layered-spinel composite phase anode material.
2. The method of manufacturing according to claim 1, characterized in that: m is one or more of Mn, ni and Co; n is one or more of Ni and Co.
3. The method of manufacturing according to claim 1, characterized in that: in step (1), the Li 2 MnO 3 The base oxide is pure phase Li 2 MnO 3 And Li (lithium) 2 MnO 3 At least one of the doping materials.
4. The method of manufacturing according to claim 1, characterized in that: in the step (1), the soluble M salt is at least one of nitrate and acetate of M; the soluble N salt is at least one of nitrate and acetate of N.
5. The method of manufacturing according to claim 1, characterized in that: in the step (1), the non-acidic solution is at least one of a neutral solution and an alkaline solution.
6. The method of manufacturing according to claim 5, wherein: the non-acidic solution is a neutral solution.
7. The method of manufacturing according to claim 6, wherein: the neutral solution is at least one of water and ethanol.
8. The method of manufacturing according to claim 7, wherein: the neutral solution is water.
9. The method of manufacturing according to claim 5, wherein: the alkaline solution is ammonia water.
10. The preparation method according to any one of claims 1 to 9, characterized in that: in the step (2), the roasting temperature is 500-950 ℃ and the roasting time is 2-24h.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311532A (en) * | 2013-05-24 | 2013-09-18 | 天津大学 | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure |
| CN104157831A (en) * | 2014-08-19 | 2014-11-19 | 哈尔滨工业大学 | Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof |
| WO2015139482A1 (en) * | 2014-03-17 | 2015-09-24 | 华南理工大学 | High-voltage lithium-ion battery positive electrode material having spinel structure and preparation method thereof |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
| CN107069030A (en) * | 2017-04-18 | 2017-08-18 | 湘潭大学 | A kind of preparation method of pattern and the double controllable lithium-rich manganese-based anode materials of size |
| CN107086298A (en) * | 2017-04-25 | 2017-08-22 | 中南大学 | By lithium-rich manganese-based nucleocapsid isomery lithium ion battery composite cathode material constituted with lithium manganate having spinel structure of stratiform and preparation method thereof |
| CN108767254A (en) * | 2018-05-24 | 2018-11-06 | 湘潭大学 | A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material |
-
2023
- 2023-03-28 CN CN202310310424.7A patent/CN116282231A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103311532A (en) * | 2013-05-24 | 2013-09-18 | 天津大学 | Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure |
| WO2015139482A1 (en) * | 2014-03-17 | 2015-09-24 | 华南理工大学 | High-voltage lithium-ion battery positive electrode material having spinel structure and preparation method thereof |
| CN104157831A (en) * | 2014-08-19 | 2014-11-19 | 哈尔滨工业大学 | Spinel nickel manganese acid lithium and layered lithium-rich manganese-based composite cathode material with core-shell structure and preparation method thereof |
| CN106410186A (en) * | 2016-11-17 | 2017-02-15 | 天津理工大学 | Preparation method and application of lithium-rich layered oxide cathode material |
| CN107069030A (en) * | 2017-04-18 | 2017-08-18 | 湘潭大学 | A kind of preparation method of pattern and the double controllable lithium-rich manganese-based anode materials of size |
| CN107086298A (en) * | 2017-04-25 | 2017-08-22 | 中南大学 | By lithium-rich manganese-based nucleocapsid isomery lithium ion battery composite cathode material constituted with lithium manganate having spinel structure of stratiform and preparation method thereof |
| CN108767254A (en) * | 2018-05-24 | 2018-11-06 | 湘潭大学 | A kind of surface texture and chemical composition synchronization modulation method of stratiform lithium-rich anode material |
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