CN105489899A - Lithium ion battery cathode and preparation method thereof - Google Patents
Lithium ion battery cathode and preparation method thereof Download PDFInfo
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- CN105489899A CN105489899A CN201610052527.8A CN201610052527A CN105489899A CN 105489899 A CN105489899 A CN 105489899A CN 201610052527 A CN201610052527 A CN 201610052527A CN 105489899 A CN105489899 A CN 105489899A
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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
- H01M4/64—Carriers or collectors
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
-
- 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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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 the field of lithium ion batteries, in particular to a lithium ion battery cathode and a preparation method thereof. According to the lithium ion battery cathode, a foam copper sheet serves as a current collector, and terephthalate cobalt serves as active substances. The lithium ion battery cathode is prepared from the foam copper sheet, terephthalic acid, cobalt-nitrate hexahydrate, N,N-dimethyl-formamide, anhydrous ethanol and deionized water. A hydrothermal reaction method is adopted for the preparation method, the active substances can directly grow on the surface of the foam cupper sheet and in pores, a traditional complicated coating technology is not needed, and the cathode applicable to lithium ion batteries can be further obtained. When the method is used for preparing the batteries, cost is low, operation is easy, and the prepared batteries are light and high in specific capacity.
Description
Technical field
The present invention relates to lithium ion battery preparing technical field, be specifically related to a kind of lithium ion battery negative and preparation method thereof.
Background technology
Lithium ion battery have cell voltage high, have extended cycle life, advantages of environment protection, be widely used in the various electronic portable device such as mobile phone, camera, notebook computer.But the material with carbon element theoretical specific capacity that commercial Li-ion battery negative pole adopts at present only has 372mAh/g, and easily generation organic solvent embeds altogether, the demand of growing high-energy energy-storage system can not be met, therefore nowadays people all to be devoted to research specific capacity large, stable circulation and the excellent active material of high rate performance.
The more ion cathode material lithium of current research comprises alloy-type negative electrodes material and nano-metal-oxide negative material, alloy-type negative electrodes material is as kamash alloy class, this kind of material has high specific capacity when doing lithium ion battery negative, but along with the increase of battery charging and discharging number of times, material also can cause material efflorescence because of phase change, affects its cycle performance; Nano-metal-oxide negative material is as di-iron trioxide, and cupric oxide etc., this kind of material also has high specific capacity, but its first charge-discharge capacitance loss is larger, and high rate performance is generally poor.
Metal organic frame (MOFs) is a kind of material with periodically cavernous structure, and it is formed by organic ligand and metal-ligand complex.Its synthetic method is simple, shows certain prospect in li-ion electrode materials field.But MOFs material conductivity is poor, a large amount of conductive agents need be added when preparing electrode to improve electronic conductivity.Too much conductive agent add the ratio reducing active material, be unfavorable for lightweight and the practical application of battery.
It is loaded down with trivial details that traditional handicraft makes lithium ion battery operation, needs first to prepare active material, then add binding agent respectively and conductive agent configures slurry, be coated on copper sheet, and it is even to there is crawling, the problem such as in active material drying course, easily to peel off, easily affect the performance of battery.
Summary of the invention
For the deficiencies in the prior art, the object of this invention is to provide a kind of is collector with foam copper, terephthalic acid (TPA) cobalt is the lithium ion battery negative of new active materials, use lithium ion battery negative preparation method provided by the invention simple compared to traditional handicraft, the circulating battery that lithium ion battery simultaneously can be made to prepare compared with traditional handicraft is stablized, and charge-discharge performance also has obvious lifting.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
(1) lithium ion battery negative, is characterized in that, foam copper sheet is collector, and terephthalic acid (TPA) cobalt is active material, and the surface of described foam copper sheet and the growth of hole situ have described active material.
Preferably, with the surface area of foam copper sheet for unit of measurement, on every square centimeter of foam copper sheet, the quality of active material is 0.5 ~ 4.5mg.
(2) lithium ion battery negative, is characterized in that, comprises following raw material components: foam copper sheet, terephthalic acid (TPA), cabaltous nitrate hexahydrate, DMF, absolute ethyl alcohol and deionized water.
Preferably, the mol ratio of described terephthalic acid (TPA) and cabaltous nitrate hexahydrate is 1: 1 ~ 1: 4, and the molar concentration of terephthalic acid (TPA) is 1.75mg/ml.
Preferably, the volume ratio of described DMF, absolute ethyl alcohol and deionized water is 1: 1: 1 ~ 1: 2: 3.
(3) preparation method for lithium ion battery negative, is characterized in that, comprises the following steps:
Step (1), preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 2 ~ 20MPa pressure, carry out compaction treatment, then hydrochloric acid washing foam copper sheet is used, use absolute ethanol washing foam copper sheet again, and be placed in protective atmosphere, 50 ~ 70 DEG C of oven dry, for subsequent use;
Step (2), weighs DMF, absolute ethyl alcohol and deionized water, is designated as solvent; Weigh terephthalic acid (TPA), cabaltous nitrate hexahydrate, be designated as active reaction material; And at room temperature add solvent and active reaction material successively to having in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5 ~ 2h;
Step (3), will through pretreated foam copper sheet punching, and it is inner to immerse stainless steel hydrothermal reaction kettle, sealed reactor, and stainless steel hydrothermal reaction kettle is positioned in temperature programmed control electric drying oven with forced convection, temperature control reacts, and reaction temperature is 90 ~ 160 DEG C, and the reaction time is 1 ~ 4 day;
Step (4), after reaction terminates, is down to room temperature by temperature programmed control electric drying oven with forced convection, takes out foam copper sheet, with distilled water and absolute ethanol washing, and vacuumize, to obtain final product.
Preferably, in step (1), protective atmosphere is the mist of argon gas or nitrogen or argon gas and nitrogen.
Preferably, in step (3), foam copper sheet immerses stainless steel hydrothermal reaction kettle inside in a hanging manner.
Preferably, in step (4), after reaction terminates, temperature programmed control electric drying oven with forced convection is down to room temperature according to rate of temperature fall 3 ~ 10 DEG C/h.
Preferably, in step (4), vacuum drying temperature is 30 ~ 100 DEG C, and the vacuum drying time is 6 ~ 12h.
Compared with prior art, the invention has the beneficial effects as follows:
Foam copper sheet a kind ofly in Copper substrate, is uniform-distribution with a large amount of connection or the material in non-intercommunicating pore hole, has lightweight, bigger serface, and the feature such as conduct electricity very well, and can be used as affluxion body in lithium ion batteries.The present invention adopts foam copper sheet as the collector of lithium ion battery negative, using terephthalic acid (TPA) cobalt as active material, adopts a step hydrothermal synthesis method to prepare lithium ion battery negative.First preliminary treatment is carried out to foam copper sheet, use hydrochloric acid absolute ethanol washing, wash the oxide layer on foam copper sheet surface off, terephthalic acid (TPA) cobalt active material is made just can be more easily grown directly upon between foam copper sheet surface and hole in building-up process, avoid active material in subsequent process because subsequent treatment is improper and affect that it is active, also without the need to re-using binding agent and conductive agent, economization operating procedure.Compared with traditional coating technique, the inventive method is simple, and cost of manufacture is low, and the lithium ion battery lighter weight made, stable circulation, and specific capacity is higher (uses battery specific capacity that conventional coating processes is made at 600mAhg
-1left and right, the battery specific capacity using the inventive method to make can reach 900mAhg
-1left and right).
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Fig. 1 is the high power scanning electron microscope (SEM) photograph of terephthalic acids cobalt/foam copper sheet lithium ion battery negative pole that embodiment 1 obtains.
Fig. 2 is the low power scanning electron microscope (SEM) photograph of terephthalic acids cobalt/foam copper sheet lithium ion battery negative pole that embodiment 1 obtains.
Fig. 3 is the charging and discharging curve figure of terephthalic acids cobalt/foam copper sheet lithium ion battery negative pole that embodiment 1 obtains, and wherein, 1,2,5,30 represent cycle-index, and abscissa is specific capacity, and ordinate is voltage.
Fig. 4 is the specific capacity-cycle graph of terephthalic acids cobalt/foam copper sheet lithium ion battery negative pole that embodiment 1 obtains, and abscissa is cycle-index, and ordinate is specific capacity.
Embodiment
In order to set forth the present invention better, describe content of the present invention further below in conjunction with embodiment, but the present invention is not limited to the following examples.
Embodiment 1
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 1h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 12h under 30 DEG C of conditions, to obtain final product.
Embodiment 2
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 10ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 1: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 1h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 12h under 30 DEG C of conditions, to obtain final product.
Embodiment 3
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 20ml distilled water (volume ratio is 3: 2: 2), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 1h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 12h under 30 DEG C of conditions, to obtain final product.
Embodiment 4
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 30ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 3: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 12h under 30 DEG C of conditions, to obtain final product.
Embodiment 5
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 20mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 2: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 12h under 30 DEG C of conditions, to obtain final product.
Embodiment 6
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 10MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 20mlN, dinethylformamide, 20ml absolute ethyl alcohol and 20ml distilled water (volume ratio is 1: 1: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 8h under 60 DEG C of conditions, to obtain final product.
Embodiment 7
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 70 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 8h under 60 DEG C of conditions, to obtain final product.
Embodiment 8
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 70 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 2h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 100 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethyl alcohol, vacuumize 6h under 100 DEG C of conditions, to obtain final product.
Embodiment 9
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 70 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.375g cabaltous nitrate hexahydrate (mol ratio is 1: 2), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 2h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 100 DEG C of conditions, be incubated 2 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 6h under 100 DEG C of conditions, to obtain final product.
Embodiment 10
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 60 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.765g cabaltous nitrate hexahydrate (mol ratio is 1: 4), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 2h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 8h under 60 DEG C of conditions, to obtain final product.
Embodiment 11
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 50 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.735g cabaltous nitrate hexahydrate (mol ratio is 1: 4), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 2h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 110 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 5 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 8h under 60 DEG C of conditions, to obtain final product.
Embodiment 12
(1) preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 15MPa pressure, carry out compaction treatment, then use hydrochloric acid washing foam copper sheet, then use absolute ethanol washing foam copper sheet, and be placed in protective atmosphere, 50 DEG C of oven dry, for subsequent use;
(2) at room temperature measure 30mlN, dinethylformamide, 20ml absolute ethyl alcohol and 10ml distilled water (volume ratio is 3: 2: 1), be designated as solvent; At room temperature take 0.105g terephthalic acid (TPA), 0.735g cabaltous nitrate hexahydrate (mol ratio is 1: 4), be designated as active reaction material; And solvent and active reaction material are added successively have in teflon-lined stainless steel hydrothermal reaction kettle, stir 2h;
(3) through pretreated foam copper sheet punching, and stainless steel hydrothermal reaction kettle inside will be immersed, sealed reactor, and stainless steel hydrothermal reaction kettle will be positioned in temperature programmed control electric drying oven with forced convection, under 90 DEG C of conditions, be incubated 2.75 days;
(4) after reaction terminates, with the rate of temperature fall of 3 DEG C/h, temperature programmed control electric drying oven with forced convection is dropped to room temperature, take out foam copper sheet, with distilled water and absolute ethanol washing, vacuumize 6h under 100 DEG C of conditions, to obtain final product.
Adopt lithium ion battery negative prepared by embodiment 1, test the chemical property of this battery material, its collection of illustrative plates as Figure 1-Figure 4.
By finding out between the surface that active material terephthalic acid (TPA) cobalt is grown on foam copper uniformly and hole in Fig. 1 and Fig. 2 scanning electron microscope (SEM) photograph, form the uniform integument of one deck, directly can be used as battery material.
After can finding out in Fig. 3 charging and discharging curve figure and Fig. 4 cycle performance figure that the lithium ion battery negative circulation 30 adopting the inventive method to obtain is enclosed, specific discharge capacity still can remain on 900mAhg
-1left and right, chemical property is good.
In addition, the lithium ion battery negative obtained by other embodiments, its chemical property and above-mentioned conclusion basically identical.
Although the present invention has done detailed description and quoted some optimum specific experiment examples as proof, but for those of ordinary skill in the art, obviously multiple amendment, change or replacement scheme can be made according to above-mentioned explanation, as: foam metal except foam copper sheet also can use foam nickel sheet.These replacement schemes all should be included within the protection range of claim.
Claims (10)
1. a lithium ion battery negative, is characterized in that, foam copper sheet is collector, and terephthalic acid (TPA) cobalt is active material, and the surface of described foam copper sheet and the growth of hole situ have described active material.
2. lithium ion battery negative according to claim 1, is characterized in that, with the surface area of foam copper sheet for unit of measurement, on the foam copper sheet of every square centimeter, the quality of active material is 0.5 ~ 4.5mg.
3. a lithium ion battery negative, is characterized in that, comprises following raw material components: foam copper sheet, terephthalic acid (TPA), cabaltous nitrate hexahydrate, DMF, absolute ethyl alcohol and deionized water.
4. lithium ion battery negative according to claim 3, is characterized in that, the mol ratio of described terephthalic acid (TPA) and cabaltous nitrate hexahydrate is 1:1 ~ 1:4, and the molar concentration of terephthalic acid (TPA) is 1.75mg/ml.
5. lithium ion battery negative according to claim 3, is characterized in that, the volume ratio of described DMF, absolute ethyl alcohol and deionized water is 1:1:1 ~ 1:2:3.
6. a preparation method for lithium ion battery negative, is characterized in that, comprises the following steps:
Step (1), preliminary treatment foam copper sheet: by porosity be 95 ~ 98% foam copper matrix roller press under 2 ~ 20MPa pressure, carry out compaction treatment, then hydrochloric acid washing foam copper sheet is used, use absolute ethanol washing foam copper sheet again, and be placed in protective atmosphere, 50 ~ 70 DEG C of oven dry, for subsequent use;
Step (2), weighs DMF, absolute ethyl alcohol and deionized water, is designated as solvent; Weigh terephthalic acid (TPA), cabaltous nitrate hexahydrate, be designated as active reaction material; And at room temperature add solvent and active reaction material successively to having in teflon-lined stainless steel hydrothermal reaction kettle, stir 0.5 ~ 2h;
Step (3), will through pretreated foam copper sheet punching, and it is inner to immerse stainless steel hydrothermal reaction kettle, sealed reactor, and stainless steel hydrothermal reaction kettle is positioned in temperature programmed control electric drying oven with forced convection, temperature control reacts, and reaction temperature is 90 ~ 160 DEG C, and the reaction time is 1 ~ 4 day;
Step (4), after reaction terminates, is down to room temperature by temperature programmed control electric drying oven with forced convection, takes out foam copper sheet, with distilled water and absolute ethanol washing, and vacuumize, to obtain final product.
7. the preparation method of lithium ion battery negative according to claim 6, is characterized in that, in described step (1), protective atmosphere is that argon gas is or/and nitrogen.
8. the preparation method of lithium ion battery negative according to claim 6, is characterized in that, in described step (3), foam copper sheet immerses stainless steel hydrothermal reaction kettle inside in a hanging manner.
9. the preparation method of lithium ion battery negative according to claim 6, is characterized in that, in described step (4), after reaction terminates, temperature programmed control electric drying oven with forced convection is down to room temperature according to rate of temperature fall 3 ~ 10 DEG C/h.
10. the preparation method of lithium ion battery negative according to claim 6, is characterized in that, in described step (4), vacuum drying temperature is 30 ~ 100 DEG C, and the vacuum drying time is 6 ~ 12h.
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