Lithium ion battery cathode material and its preparation method
Technical field:
The present invention relates to a kind of lithium ion battery cathode material and its preparation method, it belongs to the manufacturing technology in battery manufacturing technology field, particularly lithium battery.
Background technology:
Lithium ion battery is because operating voltage is high, volume is little, light weight, specific energy is high, temperature limit is wide, self-discharge rate is low, have extended cycle life, special advantages such as environmental pollution is little, memory-less effect, just obtains unusual swift and violent development once coming out.Even to this day, lithium ion battery has substituted NI-G, Ni-MH battery, becomes the absolute leading power supply of mobile phone, notebook computer and digital electronic goods, and other market space of constantly pushing ni-mh, nickel-cadmium cell, to the lead-acid battery challenge.
Under the exhaustion and environmental protection pressure of traditional energy, lithium ion battery is in the application that obtains aspect power and the energy storage more and more widely.The application of current lithium ion battery mainly concentrates on both direction: 1) development electric motor car, electric automobile, electric tool are with the motive-power battery of large-capacity high-power; 2) performance of the portable electronic electrical equipment compact battery in raising conventional use field; Continuation develops towards light, thin, short, little direction; Like battery of mobile phone, digital electrical apparatus battery etc., particularly along with the appearance of multifunctional intellectual mobile phone, this requirement is just more obvious further.No matter be motive-power battery, or compact battery, a very important technical indicator is all arranged, i.e. the energy density of battery.
The commercial li-ion cell negative electrode material mainly adopts carbonaceous materials such as MCMB, Delanium, modified natural graphite at present.On average about 10~25 μ m of the grain diameter of these negative materials.In the charging process of lithium ion battery; Lithium ion is owing to the restriction of the reason of aspects such as polarization, diffusion coefficient; Can't in the limited short time, diffuse to the core of negative material, the core of negative material can't be fully used, thereby causes the weight ratio capacity of negative pole can't reach the theoretical capacity 372mAh/g of graphite; Usually between 280mAh/g~360mAh/g, and then reduced the energy density of entire lithium ion battery.
Summary of the invention:
The purpose of this invention is to provide lithium ion battery cathode material and its preparation method with very high energy density.
The objective of the invention is to realize like this:
A kind of lithium ion battery negative material, it is a kind of spherical shell structure material of hollow, on the housing of the spherical shell of described hollow, is distributed with a large amount of micropores.
The external diameter of described hollow ball shell structure is 5~40 μ m.
The thickness of shell of described hollow ball shell structure is 3~20 μ m.
The described aperture that is distributed in the micropore on the hollow ball shell structure housing is 1~20nm.
A kind of manufacturing approach of described lithium ion battery negative material, this method comprises the steps:
A: nuclear fixing: in-10 ℃~0 ℃ temperature range; Thermosetting epoxy resin and low temperature curing agent T-31 modified amine are evenly mixed with the ratio of 100: 15~50 ratio of weight and number; Get 10 parts in this mixture then, be dissolved in 10~90 parts of acetone, add ice particulate stirring and evenly mixing in agitating device that 2~50 parts of particle diameters are about 2~20 μ m again; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 50~200 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 20~50%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 8~48 hours after rising to 80~100 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 0.2~4 hour after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 350~500 ℃ with the programming rate of 1~5 ℃/min; Constant temperature is 1~12 hour after rising to 800~1500 ℃ with the programming rate of 5~10 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
The described spherical shell structure that obtains through the D step carries out graphitization processing again under 2400~3200 ℃ of high temperature, make the composite graphite negative electrode material that the spherical shell structure material becomes.
The manufacturing approach of described lithium ion battery negative material, this method comprises the steps:
A: nuclear fixing: under 0 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 50 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 90 parts of acetone, add ice particulate stirring and evenly mixing in agitating device that 50 parts of particle diameters are about 2~20 μ m again; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 200 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 50%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 8 hours after rising to 100 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 4 hours after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 500 ℃ with the programming rate of 5 ℃/min; Constant temperature is 12 hours after rising to 1500 ℃ with the programming rate of 10 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
The manufacturing approach of described lithium ion battery negative material, this method comprises the steps:
A: nuclear fixing: under-10 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 15 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 10 parts of acetone, add 2 parts of particle diameters again and be about ice particulate stirring and evenly mixing in agitating device of 2~20; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 50 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 20%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 48 hours after rising to 80 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 0.2 hour after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 350 ℃ with the programming rate of 1 ℃/min; Constant temperature is 1 hour after rising to 800 ℃ with the programming rate of 5 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
The manufacturing approach of described lithium ion battery negative material, this method comprises the steps:
A: nuclear fixing: under-5 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 35 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 50 parts of acetone, add 28 parts of particle diameters again and be about ice particulate stirring and evenly mixing in agitating device of 2~20; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 130 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 35%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 25 hours after rising to 90 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 2 hours after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 420 ℃ with the programming rate of 3 ℃/min; Constant temperature is 6 hours after rising to 1100 ℃ with the programming rate of 8 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
Beneficial effect of the present invention: the prepared lithium cell cathode material of the present invention is the hollow shell spherical structure; In the process of charging and discharging; Lithium ion can diffuse to the innermost layer of negative material, and negative material is fully utilized, thus its capacity can reach graphite theoretical capacity 372mAh/g in addition more than.In addition, be distributed with a large amount of nano-pores on the prepared lithium cell cathode material housing of the present invention, this has guaranteed that when large current charge lithium ion has enough diffusion admittances to diffuse to the innermost layer.The graphite cathode material lithium ion battery weight reduction significantly of using the present invention to produce, the energy density of raising lithium ion battery.
Description of drawings:
Fig. 1 is a structural representation of the present invention
Embodiment:
Below in conjunction with embodiment the present invention is further explained:
Embodiment 1:
In the present embodiment, manufacturing approach of the present invention comprises the steps:
A: nuclear fixing: under 0 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 50 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 90 parts of acetone, add 50 parts of particle diameters again and be about ice particulate stirring and evenly mixing in agitating device of 2~20; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate; This shell is actual in examining fixed bed 4.
B: the preparation of shell: prepare 200 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 50%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 8 hours after rising to 100 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 4 hours after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 500 ℃ with the programming rate of 5 ℃/min; Constant temperature is 12 hours after rising to 1500 ℃ with the programming rate of 10 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
The described spherical shell structure that obtains through the D step carries out graphitization processing again under 2400~3200 ℃ of high temperature, make the composite graphite negative electrode material that the spherical shell structure material becomes.
The concrete structure of the lithium cell cathode material of the spherical shell structure that process this method obtains is:
It is a kind of spherical shell structure material of hollow; On the housing 1 of the spherical shell of described hollow 3, be distributed with a large amount of micropore 2; The external diameter of hollow ball shell structure is 5~40 μ m; The thickness of shell of hollow ball shell structure is 3~20 μ m, and the aperture that is distributed in the micropore on the hollow ball shell structure housing is 1~20nm.The aperture of micropore differs in size.
Embodiment 2:
In the present embodiment, manufacturing approach of the present invention comprises the steps:
A: nuclear fixing: under-10 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 15 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 10 parts of acetone, add ice particulate stirring and evenly mixing in agitating device that 2 parts of particle diameters are about 2~20 μ m again; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 50 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 20%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 48 hours after rising to 80 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 0.2 hour after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 350 ℃ with the programming rate of 1 ℃/min; Constant temperature is 1 hour after rising to 800 ℃ with the programming rate of 5 ℃/min again; And then being cooled to room temperature, the material of spherical shell structure that present embodiment obtains is compound carbon cathode material.
The structure of the hollow ball shell structure material that has micropore in the present embodiment is identical with embodiment 1.
Embodiment 3:
In the present embodiment, manufacturing approach of the present invention comprises the steps:
A: nuclear fixing: under-5 ℃ of temperature; Thermosetting epoxy resin is evenly mixed with the ratio of 100: 35 ratio of weight and number with low temperature curing agent T-31 modified amine; Get 10 parts in this mixture then, be dissolved in 50 parts of acetone, add ice particulate stirring and evenly mixing in agitating device that 28 parts of particle diameters are about 2~20 μ m again; Stirring is until the solidification process volatilization of acetone at mixture; Granulation, obtaining with thermosetting epoxy resin and T-31 modified amine product is shell, is " shell/nuclear 1 " structure of nuclear with the ice particulate;
B: the preparation of shell: prepare 130 parts acetone mixed solution, the mixed solution that described acetone mixed solution is made up of pitch and acetone, the melting concn of its medium pitch and acetone are 35%wt.; 10 parts of " shells/nuclear 1 " that obtain through steps A are added in whipping process in the acetone mixed solution; Granulation under the effect of continuous whipping process and evaporation acetone; Acquisition is a shell with pitch and epoxy resin and T-31 modified amine product, is " shell/nuclear 2 " structure of nuclear with the ice particulate;
C: microcellular structure preparation: will pass through " shell/nuclear 2 " water in air bath heating that step B obtains; Kept constant temperature 25 hours after rising to 90 ℃ with the programming rate of 1 ℃/min; The nuclear ice pellets of " shell/nuclear 2 " is melted; Evaporation forms a large amount of microcellular structures on housing, obtain the spherical shell structure with pitch and epoxy resin and T-31 modified amine product;
D: heat treatment: constant temperature is 2 hours after will passing through spherical shell structure that step C obtains and in the high temperature furnace that is connected with high-purity argon gas or high pure nitrogen, rising to 420 ℃ with the programming rate of 3 ℃/min; Constant temperature is 6 hours after rising to 1100 ℃ with the programming rate of 8 ℃/min again; And then be cooled to room temperature, obtain the compound carbon cathode material of spherical shell structure.
The structure of the hollow ball shell structure material that has micropore in the present embodiment is identical with embodiment 1.