CN113178569A - Preparation method of pillared layer carrier semiconductor type natural graphite composite lithium battery negative electrode material - Google Patents
Preparation method of pillared layer carrier semiconductor type natural graphite composite lithium battery negative electrode material Download PDFInfo
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- CN113178569A CN113178569A CN202110324768.4A CN202110324768A CN113178569A CN 113178569 A CN113178569 A CN 113178569A CN 202110324768 A CN202110324768 A CN 202110324768A CN 113178569 A CN113178569 A CN 113178569A
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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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
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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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- 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 natural graphite composite lithium battery cathode material and a preparation method thereof, wherein the cathode material is prepared by rutile phase TiO2Pillared graphite, specifically rutile-phase TiO pillared between layers of graphite2. The lithium battery cathode material and the preparation thereof can realize the graphite and rutile phase TiO of the cathode material through the improvement of the supporting structure2The stability of the cathode material is improved, and the performance of the cathode material of the composite lithium battery is improved.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a preparation method of a pillared layer carrier semiconductor type natural graphite composite lithium battery cathode material.
Background
The pillared layered mineral composite material refers to a composite material which has various special properties because two or more inorganic and organic pillared molecules or ions enter an interlayer domain environment and jointly act on a layered mineral pillared body and show a synergistic effect. China's porcelain is about the first appearance of the layered mineral intercalation pillared composite material. This is the intercalation and pillaring action of alkali metal ions in naturally occurring layered minerals such as feldspar or kaolinite. Certain solids having a layered structure, such as graphite, silicates, transition metal disulfides, and the like, can form intercalated pillared reactions with certain metals, acids, or bases.
Because the intercalation pillared compound shows a plurality of unique properties in the fields of superconductivity, magnetism, catalysis, battery electrode materials and the like, the interlayer pillared research is also an active research direction at present.
The principle is as follows: crystals formed by regular arrangement of atoms in layers are called lamellar crystals. Minerals with a layered crystal structure are called layered minerals. The same-layer atom spacing of the layered minerals is small, and the interaction force is strong; the atomic distance between layers in the extension direction is large and the acting force is weak. Such structures are like graphite. In addition to graphite, a large number of inorganic solids, such as layered transition metal oxides, sulfides, halides, oxyhalides, layered silicates, zeolites and alloys, can be used as the matrix for the interlayer reaction.
In the graphite crystal structure, atoms in the sheet layers are connected by covalent bond metal bonds, and the layers are combined by weaker molecular bonds, so that the physical properties of the intercalated pillared layers of the layered graphite are determined, and the pillared graphene with self-dispersion and non-stacking characteristics is prepared by researching composition work of Zhang Qiang and Weifei professor of Qinghua university in 3 months of 2014. When the pillared graphene is used for the positive electrode of a lithium-sulfur battery, the energy density and the power density of the material are obviously superior to those of the positive electrode material used for commercial lithium ion batteries, and the pillared graphene has potential application prospects in electric automobiles, personal electronic products and large-scale energy storage.
However, the study is to modulate the topological structure of graphene by catalytic vapor phase growth, and graphene with a protruding structure is obtained. Although the intercalation pillared reaction, the reaction causes a structural change between graphene layers, resulting in a protruding structure, one of which; secondly, the results of the research are applied to the positive electrode material of the battery, and do not meet the use of the negative electrode material, so a new negative electrode material for the battery is needed to meet the requirement of the negative electrode of the battery.
Disclosure of Invention
In order to solve the above problems, the primary object of the present invention is to provide a natural graphite composite lithium battery negative electrode material and a preparation method thereof, wherein the lithium battery negative electrode material and the preparation method thereof can realize graphite and rutile phase TiO of the negative electrode material by improving a support structure2The stability of the cathode material is improved, and the performance of the cathode material of the composite lithium battery is improved.
In order to achieve the above object, the technical solution of the present invention is as follows.
A natural graphite composite negative electrode material for lithium battery is prepared from rutile-phase TiO2By pillared graphite with rutile TiO phase between layers2。
A preparation method of a natural graphite composite lithium battery negative electrode material comprises the following steps:
s1, preparing graphite suspension;
grinding graphite, and dispersing by using distilled water to prepare graphite suspension;
specifically, 2g of graphite was ground and sieved with a 200-mesh sieve, and then placed in a 400ml beaker, 200ml of redistilled water was slowly added thereto, and stirred at normal temperature for 5 hours to be uniformly dispersed, thereby preparing a graphite suspension having a concentration of 1 wt%.
S2, preparing a pillared material;
adopting a liquid phase synthesis method, taking butyl titanate as a precursor, and adding the same proportion of butyl titanate into absolute ethyl alcohol under the condition of continuously stirring; after butyl titanate and absolute ethyl alcohol are uniformly mixed, slowly adding a certain amount of ammonia water (1/2-1 of the weight of butyl titanate), centrifuging and washing the solution for a plurality of times to ensure that the butyl titanate fully reacts to obtain titanium ion composite liquid; then HNO3 dissolved with graphite (or not dissolved) is added;
when adding HNO3 dissolved with graphite, firstly preparing graphite suspension and HNO3 according to the weight ratio of 1: 1.2-1.5, uniformly mixing, adding into titanium ion complex liquid, and compounding; when HNO3 which does not dissolve graphite is added, graphite and HNO 31: 1.2-1.5 are added into the titanium ion composite liquid according to the weight ratio respectively.
Then refluxing for 3-4h at a certain temperature (20-30 ℃); and aging for 24h, and drying at 65 ℃ to obtain rutile-phase TiO2 pillared graphite.
The graphite is graphene, specifically, the purity of the graphene is higher than 80%, the graphene is mainly one or more of montmorillonite, rectorite and saponite, and the graphene is crushed and ground to particles of 180 meshes and 220 meshes to obtain layered graphene powder.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the layered mineral is modified by means of doping column support, so that the stability of the negative electrode material of the lithium battery can be compounded, and the performance of the negative electrode material of the lithium battery is greatly improved.
(2) Under the condition of room temperature, the pillared layered mineral is formed by using low-cost butyl titanate as a precursor and graphite and HNO3, and the pillared composite material has high thermal stability.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The natural negative electrode material is often used for lithium batteries, and the current mainstream negative electrodes are still natural graphite and artificial graphite. The natural graphite is suitable for the lithium ion dragging and embedding and shuttling in the graphite due to the complete graphite lamellar structure, but the unmodified natural graphite has poor cycle performance, low initial coulombic efficiency and poor rate capability.
TiO2 is a semiconductor with excellent photoelectric activity, chemical stability and non-toxic physicochemical properties, and has three crystal phases of rutile phase, anatase phase and brookite phase at normal temperature as a homogeneous polymorphic form.Different crystal phases and different band gaps and crystal structures exist, so that the photocatalytic activities are different. The brookite is unstable and has low research value. The band gap of the rutile phase is higher than that of the anatase phase, so that the photocatalytic activity of the rutile phase is higher than that of the anatase phase. The titanium dioxide in rutile has the internal pore diameter of 0.27-0.98 nm, is in crystal arrangement and weak in electric property, and can greatly promote the intercalation and shuttling of lithium ions. Therefore, the inventor creatively converts rutile phase TiO2Combined with graphite to support rutile phase TiO between graphite layers2Using rutile phase TiO2The structure of the graphite is improved, thereby greatly improving the performance of the graphite.
Based on the structure, the natural graphite composite lithium battery cathode material realized by the invention is prepared by rutile phase TiO2The core structure is that rutile phase TiO is pillared between layers of graphite2。
To achieve pillared rutile TiO phases between the graphite layers2The invention also provides a preparation method of the natural graphite composite lithium battery negative electrode material, which comprises the following steps:
s1, preparing graphite suspension;
grinding graphite, and dispersing by using distilled water to prepare suspension;
specifically, 2g of graphite was ground and sieved with a 200-mesh sieve, and then placed in a 400ml beaker, 200ml of redistilled water was slowly added thereto, and stirred at normal temperature for 5 hours to be uniformly dispersed, thereby preparing a graphite suspension having a concentration of 1 wt%.
S2, preparing a pillared material;
adopting a liquid phase synthesis method, taking butyl titanate as a precursor, and adding the same proportion of butyl titanate into absolute ethyl alcohol under the condition of continuously stirring; after butyl titanate and absolute ethyl alcohol are uniformly mixed, slowly adding a certain amount of ammonia water (1/2-1 of the weight of butyl titanate), centrifuging and washing the solution for a plurality of times to ensure that the butyl titanate fully reacts to obtain titanium ion composite liquid; then HNO3 dissolved with graphite (or not dissolved) is added;
when adding HNO3 dissolved with graphite, firstly preparing graphite suspension and HNO3 according to the weight ratio of 1: 1.2-1.5, uniformly mixing, adding into titanium ion complex liquid, and compounding; when HNO3 which does not dissolve graphite is added, graphite and HNO 31: 1.2-1.5 are added into the titanium ion composite liquid according to the weight ratio respectively.
Then refluxing for 3-4h at a certain temperature (20-30 ℃); and aging for 24h, and drying at 65 ℃ to obtain rutile-phase TiO2 pillared graphite.
Usually, the graphite is graphene, the purity of the graphene is higher than 80%, the graphene is mainly mixed graphene of one or more of montmorillonite, rectorite and saponite, and the graphene is crushed and ground to particles of 180 meshes and 220 meshes to obtain layered graphene powder.
In summary, the invention has the following advantages and beneficial effects:
(1) the layered mineral is modified by means of doping column support, so that the stability of the negative electrode material of the lithium battery can be compounded, and the performance of the negative electrode material of the lithium battery is greatly improved.
(2) Under the condition of room temperature, the pillared layered mineral is formed by using low-cost butyl titanate as a precursor and graphite and HNO3, and the pillared composite material has high thermal stability.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. The natural graphite composite lithium battery cathode material is characterized in that the material is prepared by rutile phase TiO2By pillared graphite with rutile TiO phase between layers2。
2. A preparation method of a natural graphite composite lithium battery negative electrode material is characterized by comprising the following steps:
s1, preparing graphite suspension;
grinding graphite, and dispersing by using distilled water to prepare suspension;
s2, preparing a pillared material;
adopting a liquid phase synthesis method, taking butyl titanate as a precursor, and adding the same proportion of butyl titanate into absolute ethyl alcohol under the condition of continuously stirring; after the butyl titanate and the absolute ethyl alcohol are uniformly mixed, slowly adding ammonia water, and centrifugally washing the solution for a plurality of times; then HNO3 dissolved (or not dissolved) with graphite is added;
refluxing for 3-4h at normal temperature; and aging for 24h, and drying at 65 ℃ to obtain rutile-phase TiO2 pillared graphite.
3. The method for preparing the negative electrode material of the natural graphite composite lithium battery as claimed in claim 2, wherein in the step of S1, after the graphite is ground and sieved by a 200-mesh sieve, the secondary distilled water is added and stirred at normal temperature to be uniformly dispersed, and the graphite suspension with the concentration of 0.8 to 1.5 wt% is prepared.
4. The method for preparing the negative electrode material of the natural graphite composite lithium battery as claimed in claim 2, wherein in the step S2, when HNO3 dissolved with graphite is added, the graphite suspension and HNO3 are prepared according to the weight ratio of 1: 1.2-1.5, and are added into the titanium ion composite liquid after being uniformly mixed for compounding; when HNO3 which does not dissolve graphite is added, graphite and HNO 31: 1.2-1.5 are added into the titanium ion composite liquid according to the weight ratio respectively.
5. The method for preparing the negative electrode material of the natural graphite composite lithium battery as claimed in claim 2, wherein the graphite is graphene, the purity of the graphene is higher than 80%, the graphene is one or more of montmorillonite, rectorite and saponite, and the graphene is crushed and ground into the layered graphene powder with 180-mesh and 220-mesh particles.
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Citations (6)
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|---|---|---|---|---|
| CN103178243A (en) * | 2013-03-27 | 2013-06-26 | 北京大学 | Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material |
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| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
| US20150270534A1 (en) * | 2013-03-04 | 2015-09-24 | Sekisui Chemical Co., Ltd. | Fine particle-exfoliated graphite composite, negative electrode material for lithium ion secondary battery, and methods for producing the same, and lithium ion secondary battery |
| CN111048754A (en) * | 2019-11-30 | 2020-04-21 | 桂林理工大学 | Tin-doped rutile TiO2Preparation method and application of composite material |
-
2021
- 2021-03-22 CN CN202110324768.4A patent/CN113178569A/en active Pending
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| US20150270534A1 (en) * | 2013-03-04 | 2015-09-24 | Sekisui Chemical Co., Ltd. | Fine particle-exfoliated graphite composite, negative electrode material for lithium ion secondary battery, and methods for producing the same, and lithium ion secondary battery |
| CN103178243A (en) * | 2013-03-27 | 2013-06-26 | 北京大学 | Graphene/metal composite negative electrode material for lithium ion battery and preparation method of graphene/metal composite negative electrode material |
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| CN104577131A (en) * | 2015-01-16 | 2015-04-29 | 上海大学 | Preparation method of graphite-TiO2-B composite material |
| CN104815637A (en) * | 2015-04-02 | 2015-08-05 | 西北师范大学 | Method for hydrothermal method preparation of graphene-loaded flower-type titanium dioxide composite material |
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| LIN CHEN等: "Three-dimensional titanium dioxide/graphene hybrids with improved performance for photocatalysis and energy storage", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
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Application publication date: 20210727 |