CN116282232A - Preparation method of spinel positive electrode material - Google Patents
Preparation method of spinel positive electrode material Download PDFInfo
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- 239000011029 spinel Substances 0.000 title claims abstract description 43
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 18
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- 229910015645 LiMn Inorganic materials 0.000 claims abstract description 13
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- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
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- 229910013716 LiNi Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
- C01G53/52—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese of the type [Mn2O4]2-, e.g. Li2(NixMn2-x)O4, Li2(MyNixMn2-x-y)O4
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a preparation method of a spinel positive electrode material, which is characterized by comprising the following steps: the molecular formula of the spinel positive electrode material is LiMn 2‑x M x O 4 Wherein x is more than or equal to 0 and less than 1, M is one or more than one 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 base oxide and the soluble M 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 spinel-phase positive electrode material. The invention does not need a complex ion exchange process under an acidic condition, uses Li 2 MnO 3 The base oxide is used as a precursor and,in a non-acidic solution, the spinel-phase anode material can be obtained by simple 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 spinel positive electrode material.
Background
With the rapid development of science and technology, the demand of science and technology for energy is increasing, and traditional fossil energy sources such as coal, petroleum and the like are gradually exhausted, so that people need to search for alternative energy sources to meet the energy demand in the future. The new energy is regarded as clean energy, and is paid attention to because of the characteristics of being renewable, environment-friendly, pollution-free and the like. The Lithium Ion Battery (LIBS) is a novel green environment-friendly battery developed at the end of the twentieth century, and rapidly becomes a main power source of mobile phones, notebook computers, electric automobiles and the like due to the characteristics of high energy density, long service life, no memory effect and the like. In lithium ion batteries, the most central part is considered to be the positive electrode material, which is the key to reduce the cost and improve the battery performance.
From the aspects of increasing energy demand, safety, large-scale popularization and use and the like, the manganese spinel anode material taking Mn as the transition metal is widely paid attention to. Wherein, liMn 2 O 4 The composite material has the advantages of low cost, three-dimensional ion diffusion channel, good multiplying power performance and room temperature cycling stability, and a voltage platform higher than 3.9V, can bear quick charge and high working voltage, and is one of candidate materials of the anode materials for supplying power to the electric automobile. But also has some defects, mn in the material 3+ Jahn-teller distortion occurs, which causes the grains to have cubic phase to tetragonal phase transformation, thereby destroying the positive electrode material structure. To reduce Mn in the host material 3+ Induced J-T effect based on LiMn 2 O 4 Different spinel derivatives have been developed. One of the most popular derivatives is Ni-doped high voltage materialMaterial LiMn 1.5 Ni 0.5 O 4 Compared with the lithium manganate anode material, the cycling stability of the lithium manganate anode material in a high-temperature environment is obviously improved. At present, the synthesis methods of spinel cathode materials are roughly divided into two types, wherein the first type is to prepare oxide precursors first, and lithiate the oxide precursors at high temperature to obtain the cathode materials, and the methods comprise a hydrothermal method, a coprecipitation method and the like; the second type is to mix the raw materials uniformly and sinter them at high temperature to obtain the anode material, and the method includes solid phase method, sol-gel method, etc. The preparation method has various advantages, but has some defects, such as insufficient performance of the preparation material of the solid phase method, difficult precise control of the proportion of Ni/Mn components in the coprecipitation method due to different precipitation rates, and high cost of the sol-gel method, and difficult large-scale application.
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 + Thereby forming a spinel positive electrode material. The ion exchange synthesis method can select various metal cations to realize controllable composition, and meanwhile, the prepared positive electrode material has the characteristics of good capacity, good voltage stability and the like, but also 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 spinelle positive electrode material which is mild and simple in process and can be scaled, does not need a complex ion exchange process under an acidic condition, uses Li 2 MnO 3 The base oxide is a precursor, and the spinel anode material can be obtained by simply mixing, drying and roasting in a non-acidic solution (or medium), and has excellent electrochemical performance.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
preparation method of spinel positive electrode material, wherein molecular formula of spinel positive electrode material is LiMn 2- x M x O 4 Wherein x is more than or equal to 0 and less than 1, M is one or more than one 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 base oxide and the soluble M 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 spinel-phase positive electrode material.
Preferably, the M 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 step (1), the soluble M salt is at least one of volatile salts such as nitrate and acetate of M.
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 unexpectedly, the spinel positive electrode material can be obtained by simply mixing, drying and roasting in a non-acidic solution, and has excellent electrochemical performance. 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 spinel material prepared by the invention has excellent electrochemical performance, especially at a high multiplying power of 50 ℃, and still has ultrahigh specific discharge capacity and excellent cycle performance.
Drawings
FIG. 1 shows the spinel positive electrode material LiMn prepared in example 1, example 2 and comparative example 1 of the present invention 1.5 Ni 0.5 O 4 X-ray diffraction pattern of (2);
FIG. 2 shows a spinel LiMn as a cathode material prepared in example 1 of the present invention 1.5 Ni 0.5 O 4 Is a transmission electron microscope image;
FIG. 3 shows the spinel LiMn of the positive electrode materials prepared in example 1, example 1 and comparative example 1 of the present invention 1.5 Ni 0.5 O 4 A charge-discharge curve graph of (2);
FIG. 4 shows the spinel LiMn of the positive electrode materials prepared in example 1, example 2 and comparative example 1 according to the present invention 1.5 Ni 0.5 O 4 Is a cyclic performance graph of (2);
FIG. 5 shows the spinel LiMn of the positive electrode materials prepared in example 1, example 2 and comparative example 1 according to the present invention 1.5 Ni 0.5 O 4 Is a ratio performance graph of (2);
FIG. 6 shows a spinel LiMn as a cathode material prepared in example 3 of the present invention 2 O 4 An XRD pattern of (b);
FIG. 7 shows the spinel LiMn of the positive electrode materials prepared in example 3, example 4 and comparative example 2 according to the present invention 2 O 4 A charge-discharge curve graph of (2);
FIG. 8 shows a spinel LiMn as a cathode material prepared in example 3 of the present invention 2 O 4 Is multiple of (2)Rate performance graph.
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) Spinel cathode material LiMn 1.5 Ni 0.5 O 4 Is prepared from the following steps: accurately weighing Li according to the stoichiometric ratio of Li to Mn to Ni=1:1.5:0.5 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O and Ni (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 800 ℃ to finally obtain spinel anode material LiMn 1.5 Ni 0.5 O 4 Recorded as LNMO.
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) Spinel cathode material LiMn 1.5 Ni 0.5 O 4 Is prepared from the following steps: accurately weighing Li according to the stoichiometric ratio of Li to Mn to Ni=1:1.5:0.5 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O and Ni (NO) 3 ) 2 ·6H 2 Placing O in a 100mL beaker, adding 40mL25% ammonia water, magnetically stirring and mixing uniformly, placing in a 80 ℃ blast drying oven for drying for 12h, placing the obtained mixed powder in a corundum crucible, and placing in a horseCalcining for 6 hours at 800 ℃ in a furfure furnace to finally obtain LiMn 1.5 Ni 0.5 O 4 Spinel cathode material, denoted LNMO-1.
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) Spinel cathode material LiMn 1.5 Ni 0.5 O 4 Is prepared from the following steps: accurately weighing Li according to the stoichiometric ratio of Li to Mn to Ni=1:1.5:0.5 2 MnO 3 、Mn(NO 3 ) 2 ·4H 2 O and Ni (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 12h, placing the obtained mixed powder in a corundum crucible, placing in a muffle furnace for calcining for 6h at 800 ℃ to finally obtain LiMn 1.5 Ni 0.5 O 4 Spinel cathode material, denoted LNMO-2.
XRD tests showed that all three samples exhibited a typical cubic spinel structure, with a space group of Fd-3m, as shown in FIG. 1.
Transmission electron microscopy showed that clear lattice fringes were visible through the transmission electron microscopy plot as shown in fig. 2, with the 0.481nm crystal plane fringes corresponding to the (311) crystal plane in the spinel structure.
It was confirmed from EDS that the Mn, ni and O elements in the material were uniformly distributed.
As shown in FIG. 3, in the voltage interval of 3.0-4.9V, a significant voltage plateau is provided at-4.0V in the charging curve, corresponding to Mn 3+ /Mn 4+ A redox couple; two obvious spinel phase charge-discharge platforms are arranged at 4.7V and correspond to Ni 2+ /Ni 3+ /Ni 4+ A redox couple. The LNMO sample has a first discharge capacity of 130mAhg -1 The first coulombic efficiency was 80%.
Fig. 4 is a graph of the cycling performance of the materials prepared in example 1, example 2 and comparative example 1, showing that the capacity retention of LNMO after 500 cycles at a current density of 1C is 84%.
FIG. 5 is a graph showing the rate performance of the materials prepared in example 1, example 2 and comparative example 1, wherein LNMO still has 106mAhg at a high current density of 50C -1 Is a specific discharge capacity of (a).
FIGS. 3,4 and 5 show that spinel anode material LiNi having excellent electrochemical performance can be successfully obtained by using the preparation method of the present invention, i.e., under both neutral and alkaline solution conditions 0.5 Mn 1.5 O 4 . The positive electrode material (LNMO) prepared in the neutral solution has larger discharge specific capacity, good rate capability and better cycle performance than the positive electrode material (LNMO-2) prepared in the acid solution.
Example 3
(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) Spinel cathode material LiMn 2 O 4 Is prepared from the following steps: accurately weighing Li according to stoichiometric ratio Li:Mn=1:2 2 MnO 3 And Mn (NO) 3 ) 2 ·4H 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 spinel anode material LiMn 2 O 4 And is denoted as LMO.
Example 4
(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) Spinel cathode material LiMn 2 O 4 Is prepared from the following steps: accurately weighing Li according to stoichiometric ratio Li:Mn=1:2 2 MnO 3 And Mn (NO) 3 ) 2 ·4H 2 O, placing the mixture into a 100mL beaker, adding 40mL of 25% ammonia water, magnetically stirring and uniformly mixing, placing the mixture into a blast drying oven at 80 ℃ for drying for 12 hours, placing the obtained mixed powder into a corundum crucible, placing into a muffle furnace for calcining at 750 ℃ for 6 hours, and finally obtaining LiMn 2 O 4 Spinel positive electrode material, denoted LMO-1.
Comparative 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) Spinel cathode material LiMn 2 O 4 Is prepared from the following steps: accurately weighing Li according to stoichiometric ratio Li:Mn=1:2 2 MnO 3 And Mn (NO) 3 ) 2 ·4H 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 12h, placing the obtained mixed powder in a corundum crucible, placing in a muffle furnace for calcining for 6h at 750 ℃ to finally obtain LiMn 2 O 4 Spinel positive electrode material, denoted LMO-2.
XRD tests showed that, as shown in FIG. 6, the prepared sample was mixed with lithium manganate LiMn 2 O 4 The standard card of (2) can be well matched, and is of a typical face center cube spinel structure, and the space group is Fd-3m.
FIG. 7 is a graph showing the first charge and discharge of the samples prepared in example 3, example 4 and comparative example 2, in which two voltage plateaus exist in the voltage interval of 3.0 to 4.4V and Mn occurs at around 4.0V 3+ /Mn 4+ Is not shown, and Li + Is inserted into and removed from the housing. The first discharge specific capacity of the sample is 134mAh g -1 The first coulombic efficiency was 96%.
From the figure7 it can be seen that the spinel positive electrode material LiMn having excellent electrochemical properties can be successfully obtained by using the preparation method of the present invention, i.e., under both neutral and alkaline solution conditions 2 O 4 . The positive electrode material (LMO) prepared in the neutral solution has higher initial discharge specific capacity than the positive electrode material (LMO-2) prepared in the acid solution.
FIG. 8 is a graph showing the rate performance of the sample prepared in example 3, it can be seen that the spinel anode material LiMn prepared by the present invention 2 O 4 Has excellent rate capability, and still has 90mAhg at 50C high current density -1 Is a specific discharge capacity of (a).
Claims (10)
1. A preparation method of a spinel positive electrode material is characterized by comprising the following steps: the molecular formula of the spinel positive electrode material is LiMn 2-x M x O 4 Wherein x is more than or equal to 0 and less than 1, M 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 base oxide and the soluble M 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 spinel-phase positive electrode material.
2. The method of manufacturing according to claim 1, characterized in that: m 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.
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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| 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 |
| 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 |
| 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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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
| 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 |
| 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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