CN103682332B - Compound negative material of a kind of lithium ion battery and preparation method thereof and lithium ion battery - Google Patents
Compound negative material of a kind of lithium ion battery and preparation method thereof and lithium ion battery Download PDFInfo
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- CN103682332B CN103682332B CN201210362677.0A CN201210362677A CN103682332B CN 103682332 B CN103682332 B CN 103682332B CN 201210362677 A CN201210362677 A CN 201210362677A CN 103682332 B CN103682332 B CN 103682332B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
- H01M4/36—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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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- 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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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- H—ELECTRICITY
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- 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
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
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- 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
Embodiments provide the compound negative material of a kind of lithium ion battery, the compound negative material of described lithium ion battery comprises transient metal sulfide, and being arranged on the coating layer on described transient metal sulfide surface, described transient metal sulfide is NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more, the material of described coating layer comprises lithium titanate Li
4ti
5o
12.This lithium ion battery compound negative material capacity is high, have excellent cyclical stability and durability.The embodiment of the present invention additionally provides the preparation method of the compound negative material of this lithium ion battery, comprises the lithium ion battery of the compound negative material of this lithium ion battery.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to compound negative material of a kind of lithium ion battery and preparation method thereof and lithium ion battery.
Background technology
From last century the nineties, in numerous energy substitution products, lithium ion battery is subject to the close attention of people with features such as higher energy density, good cycle performance, memory-less effects.In the ascendant along with low-carbon economy, lithium ion battery just towards direction develop activelies such as power vehicle and electrical network energy storage, therefore, the emphasis that exploitation energy density is high, lithium ion battery that is that have extended cycle life has become industry research.
Current business-like lithium ion battery adopts carbon-based material as negative pole mostly, but there is a lot of defect in carbon-based negative electrode material, such as, first charge-discharge forms solid electrolyte interface film (SEI) and causes irreversible capacity loss, cycle performance is not enough, there are high temperature failure risk and security risk etc., these problems make carbon-based material cannot meet the demand of energy-storage battery.Also have part lithium ion battery to adopt alloy material as negative material, although alloy material has very high specific capacity, alloy material volumetric expansion is large, and cycle performance is poor, cannot meet the demand of marketization application.
In addition, employing sulphur or sulfide is also had (as NiS, FeS
2, FeS, TiS
2) material is as the lithium battery of negative pole storage lithium electrode material, these materials embedding lithium capacity is high, as NiS and FeS
2embedding lithium capacity be about 600mAh/g, but these material circulation poor-performings, reason is in charge and discharge process, easily there is reunion and its cycle performance reduced in sulfide active material, and sulfide active material is easy and electrolyte reacts and decomposes, cause reversible capacity to reduce, therefore cannot meet the high cycle performance requirement of energy-storage battery.
Summary of the invention
Given this, embodiment of the present invention first aspect provides the compound negative material of a kind of lithium ion battery, easily reunite to solve sulfide negative material, easily and electrolyte react and decompose, thus cause battery to have lower durability and the problem of cycle performance.Embodiment of the present invention second aspect provides the preparation method of the compound negative material of a kind of lithium ion battery.The embodiment of the present invention third aspect provides a kind of lithium ion battery.
First aspect, embodiments provides the compound negative material of a kind of lithium ion battery, comprises transient metal sulfide, and is arranged on the coating layer on described transient metal sulfide surface, and described transient metal sulfide is NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more, the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
Compared with prior art, the compound negative material of lithium ion battery provided by the invention by transient metal sulfide, and be arranged on transient metal sulfide surface coating layer composition, wherein, transient metal sulfide is selected from NiS(nickel sulfide), FeS
2(ferrous disulfide), FeS(ferrous sulfide), TiS
2(titanium disulfide), MoS(molybdenum sulfide) and Co
9s
8one or more in (cobalt sulfide).The embedding lithium capacity of these transient metal sulfides is high, as NiS and FeS
2embedding lithium capacity be about 600mAh/g, the compound negative material of lithium ion battery thus can be made to have higher capacity.
The material of coating layer comprises lithium titanate Li
4ti
5o
12there is following several large advantage: (1) lithium titanate is " zero strain " electrode material, according to the result of study (J.ofelectrochemicalsociety of the people such as S.Schamer, 146 (3), 1999,857,861), the lithium titanate of cubic spinel structure is in Lithium-ion embeding-deintercalation process, and lattice parameter is maximum from 8.3595
narrow down to 8.3538
, lattice constant change is very little, and change in volume is very little, maintains the structural stability of height, therefore has excellent cycle performance; (2) lithium titanate has three-dimensional lithium ion tunnel, and its lithium ion diffusion coefficient order of magnitude larger than carbon-based negative electrode material, can improve the high rate performance of lithium battery; (3) equilibrium potential of lithium titanate is about 1.55V, can lithium metal be effectively avoided to deposit, improve the security performance of lithium ion battery, simultaneously because intercalation potential is high, do not reach SEI film and form current potential, substantially there is not reduction decomposition on lithium titanate surface in electrolyte, is conducive to maintaining the stable of electrolyte, improves cycle performance.But lithium titanate specific capacity is low, utilize the battery that it makes, energy density is lower, and lithium titanate material price is more expensive simultaneously, has had a strong impact on the commercialization use that lithium titanate is the battery of negative pole.
Therefore, the present invention is by lithium titanate Li
4ti
5o
12be coated on described transient metal sulfide surface; can by coated for the avtive spot of sulfide surface; thus available protecting transient metal sulfide; prevent from transient metal sulfide and electrolyte from reacting to decompose; sulfide is stoped to be reunited; while making the compound negative material of lithium ion battery have high power capacity, possess good cyclical stability and durability.In addition, due to lithium titanate Li
4ti
5o
12have three-dimensional lithium ion tunnel, its lithium ion diffusion coefficient is large, thus can improve the high rate performance of lithium ion battery.And the intercalation potential of these transient metal sulfide materials and lithium titanate Li
4ti
5o
12close, the compound negative material of lithium ion battery thus can be made to have steadily consistent charge and discharge platform.
Preferably, the thickness of described coating layer is 50 ~ 8000nm.More preferably, the thickness of described coating layer is 1000 ~ 4000nm.
Preferably, described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
More preferably, described transient metal sulfide accounts for 60% ~ 80% of the compound negative material gross mass of described lithium ion battery.
Due to lithium titanate Li
4ti
5o
12have lower electronic conductance and ionic conductance ability, therefore in order to improve the electric conductivity of the compound negative material of described lithium ion battery, the material of described coating layer can comprise conductive additive further.
Described conductive additive is one or more in Delanium, native graphite, acetylene black, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose.Described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
The compound negative material of a kind of lithium ion battery that embodiment of the present invention first aspect provides, has high power capacity, and Stability Analysis of Structures, do not react with electrolyte, do not reunite, thus lithium ion battery finally can be made to have higher durability and cyclical stability; In addition, due to lithium titanate Li
4ti
5o
12lithium ion diffusion coefficient is large, thus can improve the high rate performance of lithium ion battery.
Second aspect, embodiments provides the preparation method of the compound negative material of a kind of above-mentioned lithium ion battery, comprises the following steps:
(1) by even for coated raw material lithium source, titanium source and transient metal sulfide to be covered dispersed with stirring in decentralized medium, slurry is made;
Described coated raw material lithium source is selected from one or more in lithium hydroxide, hydronium(ion) lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
Described coated raw material titanium source be selected from titanium dioxide, titanium tetrachloride, titanium trichloride, isopropyl titanate, butyl titanate, butyl titanate and metatitanic acid n-propyl one or more;
Described transient metal sulfide is selected from NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more;
Described decentralized medium is selected from water, N, one or more in dinethylformamide (DMF), DMA (DMAc), N-2-methyl pyrrolidone (NMP), oxolane (THF), ethanol and methyl alcohol;
(2) the described slurry obtained is carried out the compound negative material of coated obtained lithium ion battery by sol-gel process, hydro-thermal reaction method, microwave chemical method or high temperature solid-state method; The compound negative material of described lithium ion battery comprises described transient metal sulfide, and is coated on the coating layer on described transient metal sulfide surface, and the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
Preferably, the thickness of described coating layer is 50 ~ 8000nm.More preferably, the thickness of described coating layer is 1000 ~ 4000nm.
Preferably, described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
More preferably, described transient metal sulfide accounts for 60% ~ 80% of the compound negative material gross mass of described lithium ion battery.
The concrete operations of described sol-gel process are: described slurry is dry at 60 ~ 80 DEG C, obtain persursor material, described persursor material is placed in muffle furnace 500 ~ 700 DEG C sintering 1 ~ 5 hour, cools to room temperature with the furnace, namely obtain the compound negative material of lithium ion battery.
The concrete operations of described hydro-thermal reaction method are: proceed in hydrothermal reaction kettle by described slurry, hydrothermal solvent reaction 8 ~ 12h at 150 ~ 160 DEG C, obtain black precipitate, again black precipitate is placed in the Muffle furnace heat treatment 1 ~ 3h of 500 ~ 600 DEG C, cool to room temperature with the furnace, namely obtain the compound negative material of described lithium ion battery.
The concrete operations of described microwave chemical method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in industrial microwave oven, 600 ~ 800 DEG C are warmed up to 10 DEG C/min, be incubated 1 ~ 4 hour, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
The concrete operations of described high temperature solid-state method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in Muffle furnace and sinters 0.5 ~ 10 hour at 400 ~ 900 DEG C, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
Wherein, about transient metal sulfide and lithium titanate Li
4ti
5o
12concrete to describe as mentioned before, repeat no more herein.
In order to improve the electric conductivity of the compound negative material of described lithium ion battery, described coated raw material can comprise conductive additive further, namely add conductive additive in step (1), be dispersed in decentralized medium with lithium source, titanium source and transient metal sulfide to be covered, make slurry.
Described conductive additive is one or more in Delanium, native graphite, acetylene black, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose.Described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
The preparation method of the compound negative material of a kind of lithium ion battery that embodiment of the present invention second aspect provides, simple, the obtained compound negative material of lithium ion battery has high power capacity, and Stability Analysis of Structures, do not react with electrolyte, do not reunite, lithium ion diffusion coefficient is large, thus lithium ion battery can be made to have higher durability and cyclical stability, the high rate performance of lithium ion battery can be improved.
The third aspect, embodiments provides a kind of lithium ion battery, and this lithium ion battery comprises the compound negative material of lithium ion battery that embodiment of the present invention first aspect provides.
The cycle life of lithium ion battery that the embodiment of the present invention third aspect provides is long, and has excellent discharge capacity and high rate performance.
The advantage of the embodiment of the present invention will partly be illustrated in the following description, and a part is apparent according to specification, or can be known by the enforcement of the embodiment of the present invention.
Accompanying drawing explanation
Fig. 1 is the cycle performance comparison diagram of the embodiment of the present invention one and comparative example one gained lithium ion battery;
Fig. 2 is the cycle performance comparison diagram of the embodiment of the present invention two and comparative example two gained lithium ion battery;
Fig. 3 is the cycle performance comparison diagram of the embodiment of the present invention three and comparative example three gained lithium ion battery;
Fig. 4 is the cycle performance comparison diagram of the embodiment of the present invention four and comparative example four gained lithium ion battery;
Fig. 5 is the cycle performance comparison diagram of the embodiment of the present invention five and comparative example five gained lithium ion battery.
Embodiment
The following stated is the preferred implementation of the embodiment of the present invention; should be understood that; for those skilled in the art; under the prerequisite not departing from embodiment of the present invention principle; can also make some improvements and modifications, these improvements and modifications are also considered as the protection range of the embodiment of the present invention.
Embodiment of the present invention first aspect provides the compound negative material of a kind of lithium ion battery, easily reunite to solve sulfide negative material, easily and electrolyte react and decompose, thus cause battery to have lower durability and the problem of cycle performance.Embodiment of the present invention second aspect provides the preparation method of the compound negative material of a kind of lithium ion battery.The embodiment of the present invention third aspect provides a kind of lithium ion battery.
First aspect, embodiments provides the compound negative material of a kind of lithium ion battery, comprises transient metal sulfide, and is arranged on the coating layer on described transient metal sulfide surface, and described transient metal sulfide is NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more, the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
Compared with prior art, the compound negative material of lithium ion battery provided by the invention by transient metal sulfide, and be arranged on transient metal sulfide surface coating layer composition, wherein, transient metal sulfide is selected from NiS(nickel sulfide), FeS
2(ferrous disulfide), FeS(ferrous sulfide), TiS
2(titanium disulfide), MoS(molybdenum sulfide) and Co
9s
8one or more in (cobalt sulfide).The embedding lithium capacity of these transient metal sulfides is high, as NiS and FeS
2embedding lithium capacity be about 600mAh/g, the compound negative material of lithium ion battery thus can be made to have higher capacity.
The material of coating layer comprises lithium titanate Li
4ti
5o
12there is following several large advantage: (1) lithium titanate is " zero strain " electrode material, according to the result of study (J.ofelectrochemicalsociety of the people such as S.Schamer, 146 (3), 1999,857,861), the lithium titanate of cubic spinel structure is in Lithium-ion embeding-deintercalation process, and lattice parameter is maximum from 8.3595
narrow down to 8.3538
, lattice constant change is very little, and change in volume is very little, maintains the structural stability of height, therefore has excellent cycle performance; (2) lithium titanate has three-dimensional lithium ion tunnel, and its lithium ion diffusion coefficient order of magnitude larger than carbon-based negative electrode material, can improve the high rate performance of lithium battery; (3) equilibrium potential of lithium titanate is about 1.55V, can lithium metal be effectively avoided to deposit, improve the security performance of lithium ion battery, simultaneously because intercalation potential is high, do not reach SEI film and form current potential, substantially there is not reduction decomposition on lithium titanate surface in electrolyte, is conducive to maintaining the stable of electrolyte, improves cycle performance.But lithium titanate specific capacity is low, utilize the battery that it makes, energy density is lower, and lithium titanate material price is more expensive simultaneously, has had a strong impact on the commercialization use that lithium titanate is the battery of negative pole.
Therefore, the present invention is by lithium titanate Li
4ti
5o
12be coated on described transient metal sulfide surface; can by coated for the avtive spot of sulfide surface; thus available protecting transient metal sulfide; prevent from transient metal sulfide and electrolyte from reacting to decompose; sulfide is stoped to be reunited; while making the compound negative material of lithium ion battery have high power capacity, possess good cyclical stability and durability.In addition, due to lithium titanate Li
4ti
5o
12have three-dimensional lithium ion tunnel, its lithium ion diffusion coefficient is large, thus can improve the high rate performance of lithium ion battery.And the intercalation potential of these transient metal sulfide materials and lithium titanate Li
4ti
5o
12close, the compound negative material of lithium ion battery thus can be made to have steadily consistent charge and discharge platform.
The embodiment of the present invention does not limit the position of described transient metal sulfide in the compound negative material of lithium ion battery, is coated in described coating layer; The granular size of the embodiment of the present invention to described transient metal sulfide is not particularly limited, and can be coated in described coating layer.
The thickness of described coating layer is 50 ~ 8000nm.In present embodiment, the thickness of described coating layer is 1000 ~ 4000nm.
Described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
In present embodiment, described transient metal sulfide accounts for 60% ~ 80% of the compound negative material gross mass of described lithium ion battery.
Described transient metal sulfide is selected from NiS(nickel sulfide), FeS
2(ferrous disulfide), FeS(ferrous sulfide), TiS
2(titanium disulfide), MoS(molybdenum sulfide) and Co
9s
8one or more in (cobalt sulfide).When transient metal sulfide is two or more, the ratio between different transient metal sulfide is not particularly limited.
Due to lithium titanate Li
4ti
5o
12have lower electronic conductance and ionic conductance ability, therefore in order to improve the electric conductivity of the compound negative material of described lithium ion battery, the material of described coating layer can comprise conductive additive further.
Described conductive additive is one or more in Delanium, native graphite, acetylene black, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose.Described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
Described conductive additive is uniformly distributed in described coating layer, is positioned at lithium titanate Li
4ti
5o
12near material, namely conductive additive evenly mixes lithium titanate Li
4ti
5o
12in material, form mixing coating layer on described transient metal sulfide surface.
The compound negative material of a kind of lithium ion battery that embodiment of the present invention first aspect provides, has high power capacity, and Stability Analysis of Structures, do not react with electrolyte, do not reunite, thus lithium ion battery finally can be made to have higher durability and cyclical stability; In addition, due to lithium titanate Li
4ti
5o
12lithium ion diffusion coefficient is large, thus can improve the high rate performance of lithium ion battery.
Second aspect, embodiments provides the preparation method of the compound negative material of a kind of above-mentioned lithium ion battery, comprises the following steps:
(1) by even for coated raw material lithium source, titanium source and transient metal sulfide to be covered dispersed with stirring in decentralized medium, slurry is made;
Described coated raw material lithium source is selected from one or more in lithium hydroxide, hydronium(ion) lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
Described coated raw material titanium source be selected from titanium dioxide, titanium tetrachloride, titanium trichloride, isopropyl titanate, butyl titanate, butyl titanate and metatitanic acid n-propyl one or more;
Described transient metal sulfide is selected from NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more;
Described decentralized medium is selected from water, N, one or more in dinethylformamide (DMF), DMA (DMAc), N-2-methyl pyrrolidone (NMP), oxolane (THF), ethanol and methyl alcohol;
(2) the described slurry obtained is carried out the compound negative material of coated obtained lithium ion battery by sol-gel process, hydro-thermal reaction method, microwave chemical method or high temperature solid-state method; The compound negative material of described lithium ion battery comprises described transient metal sulfide, and is coated on the coating layer on described transient metal sulfide surface, and the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
The embodiment of the present invention does not limit the position of described transient metal sulfide in the compound negative material of lithium ion battery, is coated in described coating layer; The granular size of the embodiment of the present invention to described transient metal sulfide is not particularly limited, and can be coated in described coating layer.
The thickness of described coating layer is 50 ~ 8000nm.In present embodiment, the thickness of described coating layer is 1000 ~ 4000nm.
Described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
In present embodiment, described transient metal sulfide accounts for 60% ~ 80% of the compound negative material gross mass of described lithium ion battery.
Described transient metal sulfide is selected from NiS(nickel sulfide), FeS
2(ferrous disulfide), FeS(ferrous sulfide), TiS
2(titanium disulfide), MoS(molybdenum sulfide) and Co
9s
8one or more in (cobalt sulfide).When transient metal sulfide is two or more, the ratio between different transient metal sulfide is not particularly limited.
Lithium titanate Li is pressed in described coated raw material lithium source and titanium source
4ti
5o
12stoichiometric proportion add.
Described decentralized medium is selected from water, N, one or more in dinethylformamide (DMF), DMA (DMAc), N-2-methyl pyrrolidone (NMP), oxolane (THF), ethanol and methyl alcohol.When decentralized medium be two or more used in combination time, the ratio between different dispersion is not particularly limited.
The concrete operations of described sol-gel process are: described slurry is dry at 60 ~ 80 DEG C, obtain persursor material, described persursor material is placed in muffle furnace 500 ~ 700 DEG C sintering 1 ~ 5 hour, cools to room temperature with the furnace, namely obtain the compound negative material of lithium ion battery.
The concrete operations of described hydro-thermal reaction method are: proceed in hydrothermal reaction kettle by described slurry, hydrothermal solvent reaction 8 ~ 12h at 150 ~ 160 DEG C, obtain black precipitate, again black precipitate is placed in the Muffle furnace heat treatment 1 ~ 3h of 500 ~ 600 DEG C, cool to room temperature with the furnace, namely obtain the compound negative material of described lithium ion battery.
The concrete operations of described microwave chemical method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in industrial microwave oven, 600 ~ 800 DEG C are warmed up to 10 DEG C/min, be incubated 1 ~ 4 hour, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
The concrete operations of described high temperature solid-state method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in Muffle furnace and sinters 0.5 ~ 10 hour at 400 ~ 900 DEG C, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
Wherein, about transient metal sulfide and lithium titanate Li
4ti
5o
12concrete to describe as mentioned before, repeat no more herein.
In order to improve the electric conductivity of the compound negative material of described lithium ion battery, described coated raw material can comprise conductive additive further, namely add conductive additive in step (1), be dispersed in decentralized medium with lithium source, titanium source and transient metal sulfide to be covered, make slurry.
Described conductive additive is one or more in Delanium, native graphite, acetylene black, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose.Described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
Described conductive additive is uniformly distributed in described coating layer, is positioned at lithium titanate Li
4ti
5o
12near material, namely conductive additive evenly mixes lithium titanate Li
4ti
5o
12in material, form mixing coating layer on described transient metal sulfide surface.
The preparation method of the compound negative material of a kind of lithium ion battery that embodiment of the present invention second aspect provides, simple, the obtained compound negative material of lithium ion battery has high power capacity, and Stability Analysis of Structures, do not react with electrolyte, do not reunite, lithium ion diffusion coefficient is large, thus lithium ion battery can be made to have higher durability and cyclical stability, the high rate performance of lithium ion battery can be improved.
The third aspect, embodiments provides a kind of lithium ion battery, and this lithium ion battery comprises the compound negative material of lithium ion battery that embodiment of the present invention first aspect provides.
The cycle life of lithium ion battery that the embodiment of the present invention third aspect provides is long, and has excellent discharge capacity and high rate performance.
Multiple embodiment is divided to be further detailed the embodiment of the present invention below.Wherein, the embodiment of the present invention is not limited to following specific embodiment.In the scope of constant principal right, carrying out that can be suitable is changed and implements.
Embodiment one
The preparation method of the compound negative material of a kind of lithium ion battery
(1) hydronium(ion) lithia (LiOHH is taken
2o) 8.4g, titanium dioxide 20g are scattered in the deionized water of 150mL, add 2.3g acetylene black and are uniformly dispersed; Add the abundant dispersed with stirring of 89.7g nickel sulfide more even, obtain thick shape slurry;
(2) slurry drying in 110 DEG C of drying ovens is obtained persursor material, persursor material is placed in industrial microwave oven, with the ramp of 10 DEG C/min to 700 DEG C, be incubated 1 hour, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12the compound negative material of lithium ion battery of coated nickel sulfide (NiS).
The preparation method of lithium ion battery
By the compound negative material of the present embodiment gained lithium ion battery, conductive black, binding agent Kynoar PVDF, 92:4:4 mixes in N-2-methyl pyrrolidone (NMP) in mass ratio, obtain mixed slurry, mixed slurry is applied on the aluminium foil of 16um, pole piece is cut into after drying, be to electrode with lithium sheet, be assembled into CR2032 type button cell.Packaged battery carries out in the glove box of argon gas atmosphere, and electrolyte adopts 1mol/LLiPF
6eC:DMC(volume ratio be 1:1) mixed liquor, barrier film adopt Celgard2400.
Embodiment two
The preparation method of the compound negative material of a kind of lithium ion battery
(1) by dispersed for 13g lithium carbonate to (wherein the volume ratio of water and ethanol is 4:1) in 500mL water and ethanol solution, the mol ratio being 5:4 according to Ti:Li measures butyl titanate 75mL, after the dilution of 80mL absolute ethyl alcohol, be added to and be dispersed with in the ethanol water of lithium carbonate, add the abundant dispersed with stirring of 176g ferrous disulfide after stirring again even, obtain mixed slurry;
(2) slurry drying in 110 DEG C of drying ovens is obtained persursor material, be placed in muffle furnace 600 DEG C and burn 4 hours, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12coated ferrous disulfide (FeS
2) the compound negative material of lithium ion battery.
The preparation method of lithium ion battery
With embodiment one.
Embodiment three
The preparation method of the compound negative material of a kind of lithium ion battery
(1) take lithium nitrate 15.5g, titanium dioxide 20g be scattered in the deionized water of 200mL, add carbon black 1.2g and be uniformly dispersed, then add nickel sulfide 18.2g, the abundant dispersed with stirring of ferrous disulfide 18.2g evenly obtains thick shape slurry;
(2) slurry drying in 110 DEG C of drying ovens is obtained persursor material, persursor material is placed in industrial microwave oven, with the ramp of 10 DEG C/min to 650 DEG C, be incubated 2 hours, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12coated nickel sulfide (NiS) and ferrous disulfide (FeS
2) the compound negative material of lithium ion battery.
The preparation method of lithium ion battery
With embodiment one.
Embodiment four
The preparation method of the compound negative material of a kind of lithium ion battery
(1) by dispersed for 20g lithium acetate in ethanol solution, the mol ratio being 5:4 according to Ti:Li measures isopropyl titanate 107g, after the dilution of 200mL absolute ethyl alcohol, be added to and be dispersed with in the ethanol water of lithium acetate, 6.8g carbon nano-tube is added again after stirring, add 120gMoS(molybdenum sulfide again) fully dispersed with stirring is even, obtains gel-sol slurry;
(2) drying in 60 DEG C of drying ovens of gel-sol slurry is obtained persursor material, be placed in muffle furnace 650 DEG C and burn 2 hours, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12coated MoS(molybdenum sulfide) the compound negative material of lithium ion battery.
The preparation method of lithium ion battery
With embodiment one.
Embodiment five
The preparation method of the compound negative material of a kind of lithium ion battery
(1) hydronium(ion) lithia (LiOHH is taken
2o) 8.4g, titanium dioxide 20g are scattered in the deionized water of 250mL, are uniformly dispersed; Add 85.6gCo again
9s
8(cobalt sulfide) fully dispersed with stirring is even, obtains mixing material;
(2) subsequently solution is proceeded in hydrothermal reaction kettle, add 4.5g conductive acetylene black at 160 DEG C hydrothermal solvent reaction 10h, obtain black precipitate, then black precipitate be placed in the Muffle furnace heat treatment 2h of 500 DEG C, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12coated Co
9s
8the compound negative material of lithium ion battery of (cobalt sulfide).
The preparation method of lithium ion battery
With embodiment one.
Embodiment six
The preparation method of the compound negative material of a kind of lithium ion battery
(1) hydronium(ion) lithia (LiOHH is taken
2o) 16.8g, titanium dioxide 40g are scattered in the deionized water of 150mL; Add 2.5g Delanium, then add the abundant dispersed with stirring of 5.5g nickel sulfide evenly, obtain mixed slurry;
(2) slurry drying in 110 DEG C of drying ovens is obtained persursor material, persursor material is placed in industrial microwave oven, with the ramp of 10 DEG C/min to 700 DEG C, be incubated 1 hour, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12the compound negative material of lithium ion battery of coated nickel sulfide (NiS).
The preparation method of lithium ion battery
With embodiment one.
Embodiment seven
The preparation method of the compound negative material of a kind of lithium ion battery
(1) take lithium nitrate 15.5g, titanium dioxide 20g is scattered in the deionized water of 500mL, then add the abundant dispersed with stirring of ferrous disulfide 410.5g and evenly obtain thick shape slurry;
(2) slurry drying in 110 DEG C of drying ovens is obtained persursor material, persursor material is placed in industrial microwave oven, with the ramp of 10 DEG C/min to 650 DEG C, be incubated 2 hours, cool to room temperature with the furnace, obtain lithium titanate Li
4ti
5o
12coated ferrous disulfide (FeS
2) the compound negative material of lithium ion battery.
The preparation method of lithium ion battery
With embodiment one.
Comparative example one
By not coated lithium titanate Li
4ti
5o
12nickel sulfide (NiS) be assembled into lithium ion battery, method is with embodiment one.
Comparative example two
By not coated lithium titanate Li
4ti
5o
12ferrous disulfide (FeS
2) being assembled into lithium ion battery, method is with embodiment one.
Comparative example three
By not coated lithium titanate Li
4ti
5o
12nickel sulfide (NiS) and ferrous disulfide (FeS
2) mixing negative material be assembled into lithium ion battery, method is with embodiment one.
Comparative example four
By not coated lithium titanate Li
4ti
5o
12moS(molybdenum sulfide) be assembled into lithium ion battery, method is with embodiment one
Comparative example five
By not coated lithium titanate Li
4ti
5o
12co
9s
8(cobalt sulfide) is assembled into lithium ion battery, and method is with embodiment one
Lithium ion battery obtained in above embodiment and comparative example is experimental cell, for following effect example performance test.
Effect example
For the beneficial effect brought embodiment of the present invention technical scheme provides powerful support for, spy provides following performance test:
By lithium ion battery obtained in above-described embodiment and comparative example, battery performance test instrument is adopted to carry out the test of charge and discharge cycles.Test condition is: charge by voltage to 2.5V, discharges by voltage to 1.3V, and current density is 0.07mA/cm
2.
Fig. 1 is the cycle performance comparison diagram of the embodiment of the present invention one and comparative example one gained lithium ion battery.As can be seen from Figure 1, embodiment one Surface coating lithium titanate Li
4ti
5o
12the specific capacity first of the compound negative material of nickel sulfide (NiS) lithium ion battery be 423mAh/g, the specific capacity first of nickel sulfide (NiS) material that comparative example one is not coated is 500mAh/g, but it is after 50 circulations, its specific capacity drops to 197mAh/g, only has 39.4% of specific capacity first; And Surface coating lithium titanate Li
4ti
5o
12the compound negative material of nickel sulfide (NiS) lithium ion battery, through 50 times circulation after, its specific capacity drops to 399mAh/g, is 93% of specific capacity first; Result illustrates: Surface coating lithium titanate Li
4ti
5o
12nickel sulfide material, its cycle performance obtains remarkable improvement.
Fig. 2 is the cycle performance comparison diagram of the embodiment of the present invention two and comparative example two gained lithium ion battery.As can be seen from Figure 2, embodiment two Surface coating lithium titanate Li
4ti
5o
12the specific capacity first of the compound negative material of ferrous disulfide lithium ion battery be 556mAh/g, the specific capacity first of the ferrous disulfide material that comparative example two is not coated is 600mAh/g, but it is after 50 circulations, and its specific capacity drops to 125mAh/g, only has 21% of specific capacity first; And Surface coating lithium titanate Li
4ti
5o
12the compound negative material of ferrous disulfide lithium ion battery, through 50 times circulation after, its specific capacity drops to 512mAh/g, is 92% of specific capacity first; Result illustrates: Surface coating lithium titanate Li
4ti
5o
12ferrous disulfide material, its cycle performance obtains remarkable improvement.
Fig. 3 is the cycle performance comparison diagram of the embodiment of the present invention three and comparative example three gained lithium ion battery.As can be seen from Figure 3, embodiment three Surface coating lithium titanate Li
4ti
5o
12nickel sulfide and the specific capacity first of the compound negative material of ferrous disulfide lithium ion battery be 394mAh/g, the specific capacity first of the nickel sulfide that comparative example three is not coated and ferrous disulfide composite material is 500mAh/g, but it is after 50 circulations, its specific capacity drops to 165mAh/g, only has 30% of specific capacity first; And Surface coating lithium titanate Li
4ti
5o
12nickel sulfide and the compound negative material of ferrous disulfide lithium ion battery after 50 times circulate, its specific capacity drops to 370mAh/g, is 94% of specific capacity first; Result illustrates: Surface coating lithium titanate Li
4ti
5o
12nickel sulfide and ferrous disulfide material, its cycle performance obtains remarkable improvement.
Fig. 4 is the cycle performance comparison diagram of the embodiment of the present invention four and comparative example four gained lithium ion battery.As can be seen from Figure 4, embodiment four Surface coating lithium titanate Li
4ti
5o
12the specific capacity first of the compound negative material of molybdenum sulfide lithium ion battery be 324.2mAh/g, the specific capacity first of the molybdenum sulfide that comparative example four is not coated is 400mAh/g, but it is after 50 circulations, and its specific capacity drops to 145.6mAh/g, only has 36.4% of specific capacity first; And Surface coating lithium titanate Li
4ti
5o
12the compound negative material of molybdenum sulfide lithium ion battery through 50 times circulation after, its specific capacity drops to 298.5mAh/g, is 92.1% of specific capacity first; Result illustrates: Surface coating lithium titanate Li
4ti
5o
12material molybdenum sulfide, its cycle performance obtains remarkable improvement.
Fig. 5 is the cycle performance comparison diagram of the embodiment of the present invention five and comparative example five gained lithium ion battery.As can be seen from Figure 4, embodiment four Surface coating lithium titanate Li
4ti
5o
12the specific capacity first of the compound negative material of cobalt sulfide lithium ion battery be 298mAh/g, the specific capacity first of the molybdenum sulfide that comparative example four is not coated is 350mAh/g, but it is after 50 circulations, and its specific capacity drops to 73mAh/g, only has 20.8% of specific capacity first; And Surface coating lithium titanate Li
4ti
5o
12the compound negative material of cobalt sulfide lithium ion battery through 50 times circulation after, its specific capacity drops to 273mAh/g, is 91.6% of specific capacity first; Result illustrates: Surface coating lithium titanate Li
4ti
5o
12cobalt sulfide material, its cycle performance obtains remarkable improvement.
Claims (10)
1. the compound negative material of lithium ion battery, is characterized in that, comprise transient metal sulfide, and is arranged on the coating layer on described transient metal sulfide surface, and described transient metal sulfide is NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more, the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
2. the compound negative material of a kind of lithium ion battery as claimed in claim 1, is characterized in that, the thickness of described coating layer is 50 ~ 8000nm.
3. the compound negative material of a kind of lithium ion battery as claimed in claim 1, is characterized in that, described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
4. the compound negative material of a kind of lithium ion battery as claimed in claim 1, it is characterized in that, the material of described coating layer comprises conductive additive further, described conductive additive is one or more in Delanium, native graphite, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose, and described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
5. a preparation method for the compound negative material of lithium ion battery, is characterized in that, comprise the following steps:
(1) by even for coated raw material lithium source, titanium source and transient metal sulfide to be covered dispersed with stirring in decentralized medium, slurry is made;
Described coated raw material lithium source is selected from one or more in lithium hydroxide, hydronium(ion) lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium fluoride, lithium oxalate, lithium chloride and lithium acetate;
Described coated raw material titanium source be selected from titanium dioxide, titanium tetrachloride, titanium trichloride, isopropyl titanate, butyl titanate, butyl titanate and metatitanic acid n-propyl one or more;
Described transient metal sulfide is selected from NiS, FeS
2, FeS, TiS
2, MoS and Co
9s
8in one or more;
Described decentralized medium be selected from water, DMF, DMA, N-2-methyl pyrrolidone, oxolane, ethanol and methyl alcohol one or more;
(2) the described slurry obtained is carried out the compound negative material of coated obtained lithium ion battery by sol-gel process, hydro-thermal reaction method, microwave chemical method or high temperature solid-state method; The compound negative material of described lithium ion battery comprises described transient metal sulfide, and is coated on the coating layer on described transient metal sulfide surface, and the material of described coating layer comprises lithium titanate Li
4ti
5o
12.
6. the preparation method of the compound negative material of lithium ion battery as claimed in claim 5, it is characterized in that, described transient metal sulfide accounts for 10% ~ 95% of the compound negative material gross mass of described lithium ion battery.
7. the preparation method of the compound negative material of lithium ion battery as claimed in claim 5, it is characterized in that, described coated raw material comprises conductive additive further, described conductive additive is one or more in Delanium, native graphite, carbon black, carbonaceous mesophase spherules, carbon nano-tube, carbon nano-fiber, phenolic resins, sucrose, and described conductive additive accounts for 1% ~ 5% of the compound negative material gross mass of described lithium ion battery.
8. the preparation method of the compound negative material of lithium ion battery as claimed in claim 5, it is characterized in that, the concrete operations of described microwave chemical method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in industrial microwave oven, is warmed up to 600 ~ 800 DEG C with 10 DEG C/min, be incubated 1 ~ 4 hour, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
9. the preparation method of the compound negative material of lithium ion battery as claimed in claim 5, it is characterized in that, the concrete operations of described high temperature solid-state method are: described slurry is dry at 100 ~ 120 DEG C, obtain persursor material, described persursor material is placed in Muffle furnace and sinters 0.5 ~ 10 hour at 400 ~ 900 DEG C, with stove cooling, namely obtain the compound negative material of described lithium ion battery.
10. a lithium ion battery, is characterized in that, described lithium ion battery comprises the compound negative material of lithium ion battery described in any one of Claims 1 to 4.
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| PCT/CN2013/073413 WO2014048098A1 (en) | 2012-09-26 | 2013-03-29 | Composite negative electrode material for lithium ion battery, preparation method thereof and lithium ion battery |
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| JP6567546B2 (en) * | 2014-04-21 | 2019-08-28 | 厦▲門▼大学 | Sulfur-based transition metal composite negative electrode active material, corresponding negative electrode and corresponding battery |
| CN104505502B (en) * | 2014-12-26 | 2017-01-11 | 宁夏共享新能源材料有限公司 | Lithium titanate composite negative material for lithium ion battery and preparation method of lithium titanate composite negative material |
| CN104835961A (en) * | 2015-05-27 | 2015-08-12 | 厦门大学 | Transition metal sulfide coated with carbon, preparation method and application |
| DE102015210402A1 (en) * | 2015-06-05 | 2016-12-08 | Robert Bosch Gmbh | Cathode material for lithium-sulfur cell |
| CN105036182B (en) * | 2015-06-15 | 2017-03-08 | 山东玉皇新能源科技有限公司 | A kind of preparation method and applications of high-purity lithium titanate anode material |
| CN104944465B (en) * | 2015-06-15 | 2017-07-11 | 山东玉皇新能源科技有限公司 | A kind of preparation method and applications of lithium titanate anode material |
| CN106206043B (en) * | 2016-08-26 | 2018-07-27 | 中原工学院 | A kind of FeS2Nanometer rods/graphene is to electrode material and the preparation method and application thereof |
| CN106711413B (en) * | 2016-12-14 | 2019-07-19 | 合肥国轩高科动力能源有限公司 | A kind of lithium ion battery multi-walled carbon nanotube/molybdenum disulfide combination electrode and preparation method |
| JP6907677B2 (en) * | 2017-04-25 | 2021-07-21 | トヨタ自動車株式会社 | Method for Manufacturing Negative Electrode Active Material Particles for Lithium Ion Secondary Battery |
| CN107326384B (en) * | 2017-06-02 | 2019-04-05 | 浙江大学 | The composite material and preparation method and application of eight vulcanization nine cobalts and titanium dioxide |
| CN108878853B (en) * | 2018-07-11 | 2021-06-25 | 济南开发区星火科学技术研究院 | Preparation method of lithium titanate-graphene composite negative electrode material |
| CN109411239B (en) * | 2018-08-22 | 2023-10-03 | 浙江师范大学 | Cu doped Co for super capacitor 9 S 8 Simple preparation method of nanotube array |
| CN109052488B (en) * | 2018-09-05 | 2020-12-29 | 中国工程物理研究院电子工程研究所 | Cobalt disulfide material with high storage stability and preparation method and application thereof |
| CN110880588B (en) * | 2019-11-25 | 2021-03-05 | 浙江理工大学 | Titanium-cobalt composite material and preparation method and application thereof |
| CN110970229B (en) * | 2019-12-27 | 2020-11-06 | 中国地质大学（北京） | NiCo2S4@ mesophase carbon microsphere/carbon nanotube composite material and preparation method and application thereof |
| CN111977703B (en) * | 2020-08-21 | 2023-09-05 | 天目湖先进储能技术研究院有限公司 | Li 2 O、Li 2 CO 3 Coated transition metal sulfide-based positive electrode material, preparation method and application |
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Effective date of registration: 20201022 Address after: No.8, Xiaoping Avenue, Badu Economic Development Zone, Zhenze Town, Wujiang District, Suzhou City, Jiangsu Province Patentee after: TONGDING INTERCONNECTION INFORMATION Co.,Ltd. Address before: 625, room 269, Connaught platinum Plaza, No. 518101, Qianjin Road, Xin'an street, Shenzhen, Guangdong, Baoan District Patentee before: SHENZHEN SHANGGE INTELLECTUAL PROPERTY SERVICE Co.,Ltd. Effective date of registration: 20201022 Address after: 625, room 269, Connaught platinum Plaza, No. 518101, Qianjin Road, Xin'an street, Shenzhen, Guangdong, Baoan District Patentee after: SHENZHEN SHANGGE INTELLECTUAL PROPERTY SERVICE Co.,Ltd. Address before: 518129 Bantian HUAWEI headquarters office building, Longgang District, Guangdong, Shenzhen Patentee before: HUAWEI TECHNOLOGIES Co.,Ltd. |