CN111525123A - Cathode material of water-based lithium ion battery and preparation method and application thereof - Google Patents

Cathode material of water-based lithium ion battery and preparation method and application thereof Download PDF

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CN111525123A
CN111525123A CN202010354621.5A CN202010354621A CN111525123A CN 111525123 A CN111525123 A CN 111525123A CN 202010354621 A CN202010354621 A CN 202010354621A CN 111525123 A CN111525123 A CN 111525123A
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ion battery
lithium ion
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manganese
lithium
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褚卫国
谭兴华
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National Center for Nanosccience and Technology China
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C01G45/1221—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
    • C01G45/1235—Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a water system lithium ion battery anode material and a preparation method and application thereof2‑xMxO4Wherein x is more than 0 and less than or equal to 0.3, and M is at least one of lithium, nickel, aluminum, cobalt, zinc, magnesium, iron or chromium; by doping M in the anode material of the aqueous lithium ion battery, the crystal structure and the surface stability of the doped lithium manganate are improved, and Mn is reduced3+In such an amount that manganese dissolution is reduced, Jahn-teller effect is suppressed, and which is in the form of porous flakesThe micro-nano composite structure improves the conductivity of electrons and ions, and the doping and the structural characteristics of M ensure that the anode material of the aqueous lithium ion battery has excellent electrochemical performance.

Description

Cathode material of water-based lithium ion battery and preparation method and application thereof
Technical Field
The invention belongs to the field of battery materials, relates to a water system lithium ion battery anode material, and particularly relates to a water system lithium ion battery anode material, and a preparation method and application thereof.
Background
Compared with an organic carbonate battery, the water-based battery has the greatest advantages of safety, stability, environmental friendliness, lower cost and suitability for large-scale energy storage; and the water system lithium ion battery has huge application prospect in the fields of low-cost electric vehicle power supply, household energy storage and the like.
Spinel structure LiMn2O4The lithium ion battery has the outstanding advantages of high energy density, wide raw material source, low price, high safety, environmental friendliness and the like, and is widely applied to organic lithium ion batteries. The electrochemical performance of the electrochemical cell is not satisfactory, and further optimization is needed. The performance decay mechanisms in the water-based battery and the organic carbonate-based battery are different, so that the electrochemical performance of lithium manganate in the water-based battery is improved by adopting an element doping method so far, the research on the cycle performance is less, and the research on the modification mechanism of the doping element and the modification effect of different elements is not very clear.
CN108390011A discloses a lithium manganate, graphene oxide and carbon nanotube composite aerogel, a preparation method thereof and application of the aerogel as a cathode material of a water-based lithium ion battery. The material is mainly characterized in that a hydrogel precursor is formed by graphene oxide, carbon nano tubes and lithium manganate, and then the hydrogel precursor is frozen and dried to obtain the composite aerogel material. The graphene oxide in the material can construct a three-dimensional network structure with communicated inner parts, the carbon nano tubes shuttle through the network, the conductivity of the aerogel can be improved, and the lithium manganate is uniformly encapsulated in the three-dimensional network with good conductivity; CN105845972A discloses a fibrous water system lithium ion battery and a preparation method thereof. The fibrous water system lithium ion battery takes polyimide/carbon nano tube composite fiber as a negative electrode, lithium manganate/carbon nano tube fiber as a positive electrode and lithium sulfate aqueous solution as electrolyte; because of the insufficient electrochemical performance of lithium manganate, the composite material of lithium manganate and other materials is adopted as the anode material in the above documents, and the preparation cost is high.
The micro-nano composite structure formed by self-assembling nano particles can simultaneously improve electronic and ionic conductivity, and is beneficial to the performance exertion of the battery; however, the synthesis of micro-nano composite structures with special structures is difficult, and methods such as hydrothermal method and the like with low yield and unsuitability for large-scale production are usually needed. Therefore, it is also necessary to develop a method for preparing the micro-nano composite structure, which is low in cost, simple and feasible and suitable for large-scale production.
In view of this, it is still of great significance to develop a cathode material of a water system lithium ion battery and a preparation method thereof, wherein the cathode material has excellent electrochemical performance, low cost, simple and easy preparation method, and is suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a water-system lithium ion battery positive electrode material and a preparation method and application thereof2-xMxO4Wherein x is more than 0 and less than or equal to 0.3, and M is at least one of lithium, nickel, aluminum, cobalt, zinc, magnesium, iron or chromium; by doping M in the anode material of the aqueous lithium ion battery, the crystal structure and the surface stability of the doped lithium manganate are improved, and Mn is reduced3+The content of the manganese is reduced, the John-teller effect is inhibited, the electronic and ionic conductivity is improved due to the porous flaky micro-nano composite structure, and the electrochemical performance of the anode material of the aqueous lithium ion battery is excellent due to the doping of M and the structural characteristics of M.
Electrochemical performance herein refers to cycling performance, rate capability and specific capacity.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a water-based lithium ion battery cathode material, wherein the chemical formula of the water-based lithium ion battery cathode material is LiMn2-xMxO4Wherein x is more than 0 and less than or equal to 0.3, such as 0.05, 0.1, 0.2, 0.3 and the like, M is selected from at least one of lithium, nickel, aluminum, cobalt, zinc, magnesium, iron or chromium, and the anode material of the aqueous lithium ion battery is in a porous flaky micro-nano composite structure.
Where M represents a doping element.
The porous flaky micro-nano composite structure means that the water-based lithium ion battery cathode material is a micron-sized two-dimensional porous flaky structure obtained by self-assembling primary nano particles.
M in the anode material of the water-based lithium ion battery is doped with manganese sites in lithium manganate to obtain doped lithium manganate, the doped lithium manganate can obviously improve the crystal structure and surface stability of the anode material of the water-based lithium ion battery, and Mn is reduced3+Content, thereby reducing manganese dissolution and inhibiting John-teller effect; compared with a pure lithium manganate material, the anode material of the aqueous lithium ion battery provided by the invention has obviously improved cycle performance.
The pores among the particles in the porous flaky micro-nano composite structure are distributed in the range of 10nm to 500nm, such as 20nm, 50nm, 100nm, 200nm, 300nm or 400 nm.
Preferably, x is selected from 0.01-0.3, such as 0.03, 0.05, 0.06, 0.07, 0.08, 0.09, 0.1, 0.15, 0.2 or 0.2, etc., preferably 0.05-0.1.
Preferably, the crystal structure of the water-based lithium ion battery positive electrode material is a spinel structure.
Preferably, the porous flaky micro-nano composite structure is formed by self-assembly of nano particles.
The anode material of the water-based lithium ion battery is a porous nano sheet structure formed by self-assembling nano particles, can simultaneously improve electronic and ionic conductivity, and obviously optimizes the electrochemical performance of the material.
Preferably, the molar percentage of M is 0-15%, such as 0.5%, 1%, 2.5%, 4%, 5%, 7%, 10%, 12%, 14%, 14.5%, etc., based on 100% of the total molar number of manganese and the doping element M in the aqueous lithium ion battery positive electrode material.
In a second aspect, the present invention provides a method for preparing a cathode material for a water-based lithium ion battery according to the first aspect, the method including mixing a manganese source, a lithium source and an M source to obtain a metal source solution, and then performing heat treatment using expanded graphite as a template to obtain the cathode material for the water-based lithium ion battery; wherein the M source is at least one selected from a lithium source, a nickel source, an aluminum source, a cobalt source, a zinc source, a magnesium source, an iron source or a chromium source.
According to the preparation process of the anode material of the aqueous lithium ion battery, the expanded graphite is used as the template, the solid-phase sintering method is adopted to prepare the porous flaky micro-nano composite structure with the self-assembled nano particles, the porous flaky micro-nano composite structure has unique structural advantages in the aspect of optimizing the electrochemical performance of the material, the method is simple and easy to implement, the cost is low, the large-scale production is easy, and the obtained micro-nano composite structure is beneficial to the electrochemical performance of the anode material of the aqueous lithium ion battery.
The expanded graphite is used as a template, the precursor material is uniformly dispersed among the expanded graphite sheets, and the expanded graphite has a guiding effect on the morphology of the material in the sintering process, so that the obtained anode material can be ensured to be a porous flaky micro-nano composite structure formed by self-assembling primary particles.
Preferably, the method for performing heat treatment by using the expanded graphite as the template comprises the steps of injecting a metal source solution into pores of the expanded graphite, drying and sintering to obtain the anode material of the water-based lithium ion battery.
Preferably, the sintering is performed in a muffle furnace.
Preferably, the sintering comprises treating the dried product at 200-550 ℃, such as 250 ℃, 300 ℃, 350 ℃, 400 ℃, 450 ℃ or 500 ℃ and the like, and then continuing sintering at 600-900 ℃, such as 650 ℃, 700 ℃, 750 ℃, 800 ℃ or 850 ℃ and the like to obtain the anode material of the water-based lithium ion battery.
In the sintering process, the dried product is treated at the low temperature of 550 ℃ and 200 ℃ before the high-temperature (900 ℃) sintering, so that the size uniformity of the material can be improved in the process, and the performance of the material is favorably improved.
Preferably, the sintering comprises treating the dried product at 400 ℃, such as 320 ℃, 350 ℃ or 380 ℃ and the like, and then continuing sintering at 800 ℃, such as 720 ℃, 750 ℃ or 780 ℃ and the like, at 700-.
Preferably, the drying temperature is 60-100 ℃, such as 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or 95 ℃ and the like, and the drying time is 2-24h, such as 5h, 10h, 15h or 20h and the like.
Preferably, the treatment time at 200-550 ℃ is 1-10h, such as 2h, 3h, 4h, 5h, 6h, 7h, 8h or 9h, etc.
Preferably, the sintering time at 600-900 ℃ is more than 1h, such as 1h, 3h, 5h, 10h, 20h, 30h, 40h or 45h, etc., preferably 1-48 h.
Preferably, the manganese source is selected from any one of manganese bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, manganese sulfate or manganese acetate or a combination of at least two of them, the combination exemplarily comprising a combination of manganese bromide and manganese carbonate, a combination of manganese chloride and manganese oxide, a combination of manganese nitrate and manganese oxalate or a combination of manganese sulfate and manganese acetate, and the like.
Preferably, the lithium source is selected from any one of lithium carbonate, lithium hydroxide, lithium oxide, lithium oxalate, lithium acetate or lithium nitrate, or a combination of at least two thereof, which illustratively includes a combination of lithium carbonate and lithium hydroxide, a combination of lithium oxide and lithium oxalate, or a combination of lithium acetate and lithium nitrate, and the like.
Preferably, the M source is selected from at least one of chloride, sulfate, nitrate or acetate; preferably nitrate and/or chloride.
As a preferable technical solution of the present invention, the method for preparing the cathode material of the aqueous lithium ion battery comprises the steps of:
(1) fully mixing a manganese source, a lithium source and an M source to obtain a metal source solution;
(2) injecting the metal source solution in the step (1) into pores of the expanded graphite, and then drying at 60-100 ℃ for 2-24 h;
(3) and (3) placing the dried product in the step (2) in a muffle furnace, treating for 1-10h at the temperature of 200-.
In a third aspect, the present invention provides an aqueous lithium ion battery using the aqueous lithium ion battery positive electrode material according to the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the M element in the anode material of the water-based lithium ion battery is used for doping a manganese site in lithium manganate to obtain doped lithium manganate, the doped lithium manganate can obviously improve the crystal structure and surface stability of the anode material of the water-based lithium ion battery, and Mn is reduced3+Content, thereby reducing manganese dissolution and inhibiting John-teller effect; the lithium ion battery cathode material has a porous flaky porous sheet structure, so that the ionic and electronic conductivity is improved, and the cycle performance of the obtained water-based lithium ion battery cathode material is obviously improved due to the M doping and the structural characteristics of the M doping;
(2) the preparation method of the water-based lithium ion battery anode material takes the expanded graphite as a template, and adopts a solid-phase sintering method to prepare the porous sheet structure with self-assembled nano particles.
Drawings
FIG. 1 shows LiMn prepared in example 1 of the present invention1.95Li0.05O4X-ray powder diffractogram of (a);
FIG. 2 shows LiMn prepared in example 1 of the present invention1.95Li0.05O4Scanning electron micrograph (c).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The conditions for performing electrochemical performance tests on the cathode materials of the water-based lithium ion batteries in the following examples and comparative examples using the button cell are as follows:
the positive electrode materials prepared in the examples and comparative examples were used as positive electrode active materials;
the positive electrode of the button cell for electrochemical performance test is prepared by grinding and mixing a positive active material, acetylene black and PTFE according to the mass ratio of 8:1:1, dripping alcohol to dissolve a binder PTFE to obtain uniformly mixed slurry, pressing the slurry onto a stainless steel mesh, drying, weighing and placing in a glove box for later use; the electrode film has an areal density of active material greater than 2mg/cm2(ii) a Electrolyte of 2.5M Li2SO4The cathode material is active carbon, and the glass fiber membrane is a diaphragm.
Example 1
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-shaped lithium-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Li0.05O4(ii) a The preparation method comprises the following steps:
(1) dissolving lithium nitrate and manganese nitrate in water according to a stoichiometric ratio to obtain a mixed solution;
(2) injecting the mixed solution in the step (1) into pores of the expanded graphite, and drying at 80 ℃ for 5 hours to obtain a precursor;
(3) placing the precursor in the step (2) in a muffle furnace, firstly heating to 350 ℃, keeping the temperature for 4 hours, then heating to 750 ℃, keeping the temperature for 8 hours, and cooling to room temperature to obtain the porous flaky lithium-doped lithium manganate positive electrode material, and marking the material as LiMn1.95Li0.05O4。
LiMn obtained in this example1.95Li0.05O4The X-ray powder diffraction pattern of the compound is shown in figure 1, and as can be seen from figure 1, the product is of a single-phase spinel structure, and the product is high-purity LiMn1.95Li0.05O4The crystallinity is high;
LiMn obtained in this example1.95Li0.05O4The scanning electron microscope image of (a) is shown in fig. 2, and as can be seen from fig. 2, the product is a porous flaky micro-nano composite structure formed by self-assembling nano particles, and the primary particles are uniform in size.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 110mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 93%.
Example 2
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet iron-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Fe0.05O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and ferric nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 108mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention after 500 cycles was 87%.
Example 3
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-shaped nickel-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Ni0.05O4The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and nickel nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the positive electrode material obtained in the embodiment shows that when the current density is 0.1A/g, the first specific discharge capacity is 107mAh/g, and the capacity retention rate is 85% after 200 cycles. At a current density of 1A/g, the capacity retention rate after 500 cycles was 95%.
Example 4
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-shaped aluminum-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Al0.05O4The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and aluminum nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 110mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention after 500 cycles was 97%.
Example 5
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-like cobalt-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Co0.05O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and cobalt nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 113mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 94%.
Example 6
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-shaped magnesium-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.95Mg0.05O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and magnesium nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 112mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 98%.
Example 7
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet nickel and aluminum co-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.9Ni0.05Al0.05O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate, nickel nitrate and aluminum nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 105mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 98%.
Example 8
In this embodiment, the cathode material of the aqueous lithium ion battery is a porous sheet-shaped nickel-doped lithium manganate cathode material, and the chemical formula of the cathode material is LiMn1.9Ni0.1O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and nickel nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 102mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 99%.
Example 9
The chemical formula of the cathode material of the water-based lithium ion battery in the embodiment is LiMn1.8Ni0.2O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate, manganese nitrate and nickel nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 92mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 99%.
Example 10
The difference between the present embodiment and embodiment 1 is that, in step (3), the positive electrode material is obtained by first raising the temperature to 250 ℃, maintaining the temperature for 4 hours, then raising the temperature to 650 ℃, maintaining the temperature for 8 hours, and cooling to room temperature.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 103mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 85%.
Example 11
The difference between the present embodiment and embodiment 1 is that, in step (3), the temperature is raised to 450 ℃ and maintained for 4 hours, then raised to 850 ℃ and maintained for 8 hours, and cooled to room temperature to obtain the cathode material.
The result of the electrochemical performance test of the cathode material obtained in the embodiment shows that the first discharge specific capacity is 101mAh/g when the current density is 0.1A/g. At a current density of 1A/g, the capacity retention after 500 cycles was 90%.
Comparative example 1
The chemical formula of the positive electrode material in this comparative example was LiMn1.95Li0.05O4；
The difference between the comparative example and the example 1 is that the preparation method of the cathode material is a sol-gel method, and the preparation method specifically comprises the following steps:
(a) dissolving lithium nitrate and manganese nitrate into water according to a stoichiometric ratio, and then adding the following metal ions: adding citric acid according to the proportion of 1:1 of citrate radical to obtain a mixed solution;
(b) stirring the mixed solution in the step (a) at room temperature for 12 hours, evaporating the mixed solution in a water bath at 80 ℃, presintering the mixed solution at 230 ℃ for 5 hours, and fully grinding the mixed solution in a mortar to obtain a powder precursor;
(c) and (c) placing the powder precursor in the step (b) in a muffle furnace, heating to 350 ℃, keeping the temperature for 4 hours, heating to 750 ℃, keeping the temperature for 8 hours, and cooling to room temperature to obtain the cathode material.
The result of electrochemical performance test of the anode material obtained in the comparative example shows that when the current density is 0.1A/g, the first discharge specific capacity is 105 mAh/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 82%.
Comparative example 2
The chemical formula of the positive electrode material in this comparative example was LiMn2O4(ii) a The preparation method is different from that of example 1 only in that lithium nitrate and manganese nitrate are dissolved in water according to the stoichiometric ratio in step (1) to obtain a mixed solution, and other conditions and parameters are completely the same as those in example 1.
The result of electrochemical performance test of the anode material obtained in the comparative example shows that when the current density is 0.1A/g, the first discharge specific capacity is 112 mAh/g. At a current density of 1A/g, the capacity retention rate after 500 cycles was 80%.
The results of electrochemical performance tests performed on the examples and comparative examples are shown in table 1;
TABLE 1
Figure BDA0002473051150000121
As can be seen from table 1 above, the cathode material for the aqueous lithium ion battery has excellent electrochemical properties due to element doping and a porous flaky micro-nano composite structure thereof, and the doping element M is selected from at least one of lithium, nickel, aluminum, cobalt, zinc, magnesium, iron, or chromium. Under the condition that the current density is 1A/g, the capacity retention rate of the water-based lithium ion battery anode material is more than 85% after 500 cycles.
Comparing examples 3, 8 and 9 of the present invention, it can be seen that when x is 0.05 to 0.1, the electrochemical performance of the obtained cathode material of the aqueous lithium ion battery is the best, and when x is greater than 0.1, the specific discharge capacity is significantly reduced.
Comparing examples 1, 10 and 11 of the present invention, it can be seen that in the preparation process of the positive electrode material of the water-based lithium ion battery of the present invention, the positive electrode material is treated at 400 ℃ under 300-.
Comparing example 1 with comparative example 1, it can be seen that in comparative example 1, a sol-gel method is adopted, the porous flaky micro-nano composite structure of the invention cannot be obtained, and the electrochemical performance of the porous flaky micro-nano composite structure is obviously inferior to that of the anode material of the aqueous lithium ion battery of the invention.
Comparing example 1 and comparative example 2 of the present application, it can be seen that, in comparative example 2, the M element is not doped, and the cycle performance of the obtained cathode material is obviously insufficient.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (10)

1. The cathode material of the water-based lithium ion battery is characterized in that the chemical formula of the cathode material of the water-based lithium ion battery is LiMn2-xMxO4Wherein x is more than 0 and less than or equal to 0.3, M is selected from at least one of lithium, nickel, aluminum, cobalt, zinc, magnesium, iron or chromium, and the anode material of the water-based lithium ion battery is in a porous flaky micro-nano composite structure.
2. The water-based lithium ion battery positive electrode material according to claim 1, wherein the doping element M is one or two elements selected from lithium, nickel, aluminum, cobalt, zinc, magnesium, iron, and chromium;
preferably, x is selected from 0.01-0.3, preferably 0.05-0.1;
preferably, the crystal structure of the water-based lithium ion battery cathode material is a spinel structure;
preferably, the porous flaky micro-nano composite structure is formed by self-assembly of nano particles.
3. The water-based lithium ion battery positive electrode material according to claim 1 or 2, wherein the molar percentage of the doping element M is 0 to 15% based on 100% of the total molar number of manganese and the doping element M in the water-based lithium ion battery positive electrode material.
4. The method for preparing the aqueous lithium ion battery positive electrode material according to any one of claims 1 to 3, wherein the method comprises mixing a manganese source, a lithium source and an M source to obtain a metal source solution, and then performing heat treatment by using expanded graphite as a template to obtain the aqueous lithium ion battery positive electrode material; wherein the M source is at least one selected from a lithium source, a nickel source, an aluminum source, a cobalt source, a zinc source, a magnesium source, an iron source or a chromium source.
5. The preparation method according to claim 4, wherein the heat treatment method using the expanded graphite as the template comprises injecting a metal source solution into pores of the expanded graphite, drying, and sintering to obtain the aqueous lithium ion battery positive electrode material;
preferably, the sintering is carried out in a muffle furnace;
preferably, the sintering comprises treating the dried product at the temperature of 200-550 ℃, and then continuing sintering at the temperature of 600-900 ℃ to obtain the anode material of the water-based lithium ion battery;
preferably, the sintering comprises treating the dried product at 400 ℃ and 300 ℃, and then continuing sintering at 800 ℃ and 700 ℃ to obtain the cathode material of the water-based lithium ion battery.
6. The method according to claim 5, wherein the drying temperature is 60 to 100 ℃ and the drying time is 2 to 24 hours.
7. The method according to claim 5 or 6, wherein the treatment time at 200-550 ℃ is 1-10 h;
preferably, the sintering time at 600-900 ℃ is more than 1h, preferably 1-48 h.
8. The method according to any one of claims 4 to 7, wherein the manganese source is selected from any one or a combination of at least two of manganese bromide, manganese carbonate, manganese chloride, manganese oxide, manganese nitrate, manganese oxalate, manganese sulfate or manganese acetate, preferably manganese nitrate and/or manganese acetate;
preferably, the lithium source is selected from any one of lithium carbonate, lithium hydroxide, lithium oxide, lithium oxalate, lithium acetate or lithium nitrate or a combination of at least two of them, preferably lithium nitrate and/or lithium acetate;
preferably, the M source is selected from at least one of chloride, sulfate, nitrate or acetate; preferably nitrate and/or chloride.
9. The method of any one of claims 4 to 8, wherein the method comprises the steps of:
(1) fully mixing a manganese source, a lithium source and an M source to obtain a metal source solution;
(2) injecting the metal source solution in the step (1) into pores of the expanded graphite, and then drying at 60-100 ℃ for 2-24 h;
(3) and (3) placing the dried product in the step (2) in a muffle furnace, treating for 1-10h at the temperature of 200-.
10. An aqueous lithium ion battery, characterized in that the aqueous lithium ion battery employs the aqueous lithium ion battery positive electrode material according to any one of claims 1 to 3.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113293290A (en) * 2021-05-21 2021-08-24 江苏中南锂业有限公司 Electrode material for lithium extraction in salt lake and preparation method and application thereof
CN113809291A (en) * 2021-08-11 2021-12-17 桂林电子科技大学 Spinel structure positive electrode material of aluminum ion battery and preparation method and application thereof
CN114988384A (en) * 2022-05-20 2022-09-02 上海锦源晟新能源材料有限公司 Lithium manganate material, preparation method thereof and secondary battery

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101262056A (en) * 2007-03-08 2008-09-10 复旦大学 A water solution chargeable lithium ion battery
CN102364727A (en) * 2011-11-15 2012-02-29 中国东方电气集团有限公司 Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material
CN102629686A (en) * 2012-03-29 2012-08-08 郑州大学 Electrode material of drainage rechargeable and dischargeable lithium ion and aqueous solution rechargeable and dischargeable lithium ion battery
CN102881885A (en) * 2012-09-03 2013-01-16 江苏金和源新材料有限公司 Method for manufacturing lithium ion battery anode material lithium manganate for electric vehicle
CN106972171A (en) * 2017-05-08 2017-07-21 国家纳米科学中心 A kind of three-dimensional net structure material, preparation method and its usage
CN107104233A (en) * 2017-05-26 2017-08-29 国家纳米科学中心 A kind of anode material for lithium-ion batteries and preparation method thereof
CN108063246A (en) * 2017-12-11 2018-05-22 合肥国轩电池材料有限公司 A kind of preparation method of graphene template individual layer sheet lithium-rich manganese-based anode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101262056A (en) * 2007-03-08 2008-09-10 复旦大学 A water solution chargeable lithium ion battery
CN102364727A (en) * 2011-11-15 2012-02-29 中国东方电气集团有限公司 Hard carbon micro-spherical composite anode material of lithium battery and preparation method for hard carbon micro-spherical composite anode material
CN102629686A (en) * 2012-03-29 2012-08-08 郑州大学 Electrode material of drainage rechargeable and dischargeable lithium ion and aqueous solution rechargeable and dischargeable lithium ion battery
CN102881885A (en) * 2012-09-03 2013-01-16 江苏金和源新材料有限公司 Method for manufacturing lithium ion battery anode material lithium manganate for electric vehicle
CN106972171A (en) * 2017-05-08 2017-07-21 国家纳米科学中心 A kind of three-dimensional net structure material, preparation method and its usage
CN107104233A (en) * 2017-05-26 2017-08-29 国家纳米科学中心 A kind of anode material for lithium-ion batteries and preparation method thereof
CN108063246A (en) * 2017-12-11 2018-05-22 合肥国轩电池材料有限公司 A kind of preparation method of graphene template individual layer sheet lithium-rich manganese-based anode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
李伟，等: "阳离子掺杂对LiMn2O4结构和电性能的影响", 《电源技术》 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113293290A (en) * 2021-05-21 2021-08-24 江苏中南锂业有限公司 Electrode material for lithium extraction in salt lake and preparation method and application thereof
CN113293290B (en) * 2021-05-21 2022-04-12 江苏中南锂业有限公司 Electrode material for lithium extraction in salt lake and preparation method and application thereof
CN113809291A (en) * 2021-08-11 2021-12-17 桂林电子科技大学 Spinel structure positive electrode material of aluminum ion battery and preparation method and application thereof
CN113809291B (en) * 2021-08-11 2023-08-29 桂林电子科技大学 Spinel structure positive electrode material of aluminum ion battery, and preparation method and application thereof
CN114988384A (en) * 2022-05-20 2022-09-02 上海锦源晟新能源材料有限公司 Lithium manganate material, preparation method thereof and secondary battery

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