CN105655542A - A lithium ion battery anode and a preparing method thereof - Google Patents
A lithium ion battery anode and a preparing method thereof Download PDFInfo
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- CN105655542A CN105655542A CN201410649911.7A CN201410649911A CN105655542A CN 105655542 A CN105655542 A CN 105655542A CN 201410649911 A CN201410649911 A CN 201410649911A CN 105655542 A CN105655542 A CN 105655542A
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Abstract
A lithium ion battery anode is provided. The lithium ion battery anode comprises an anode coating including a carbon material, an adhesive and a conductive agent. The carbon material comprises a carbon core, a first carbon material covering the carbon core and a second carbon material covering the first carbon material, wherein the carbon core is graphite or mesocarbon microbeads, the first carbon material is hard carbon, graphene or carbon nanotubes, and the second carbon material is amorphous carbon or graphite. The porosity of the anode coating is 20-40%. The thickness of the anode coating is 40-90 mum. The carbon material with a special structure is added into the lithium ion battery anode, the porosity and the thickness which are electrode characteristic parameters are adjusted, and therefore the battery is high in energy density and power density. A preparing method of the lithium ion battery anode is also provided.
Description
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of lithium ion battery negative and preparation method thereof.
Background technology
Lithium power technology has become as the important component part of modern society, all in the portable energy source using lithium electricity to provide from smart mobile phone to electric motor car etc. Lithium ion battery is realized commercialization in 1991 by Sony the earliest, development afterwards, technically achieve significant progress, but the aspects such as the energy density of battery, power, life-span and safety yet suffer from defect, the demand of social development can not be fully met, therefore become the problem that research staff is in the urgent need to address. It is known that battery performance is heavily dependent on material technology, improving typically by improving negative pole and what positive electrode realized of battery performance.
The business-like lithium ion battery overwhelming majority adopts a certain or several material with carbon element as negative pole now. Material with carbon element in 1973 is suggested first and can be used as intercalation electrode, is widely used subsequently. Adopt different material with carbon element presoma, preparation method and heat treatment/chemistry method all can obtain the material with carbon element with different crystallinity, chemical composition and microstructure.
The material with carbon element of lithium ion intercalation mainly has graphite, coke, mesophase pitch, carbon fiber, pyrolytic carbon, carbon 60 and CNT etc. Amorphous carbon (such as soft carbon and hard carbon) is relative to crystalloid material with carbon element (such as Delanium and native graphite), more advantage in life-span, power and security performance, but graphite material is then in energy density and with the obvious advantage in price. Based on this, in order to improve the life-span of battery, power and security performance, people are often blended into soft carbon or hard carbon in graphite material and make negative pole, but the step being the increase in blending too increases production cost simultaneously. Therefore, the negative pole how manufacturing low-cost and high-performance is always up a major challenge of lithium electrician's industry.
Summary of the invention
Present invention solves the technical problem that and be in that to provide a kind of lithium ion battery negative, the lithium ion battery negative that the application provides, make lithium ion battery have higher energy density, power density and less costly.
In view of this, this application provides a kind of lithium ion battery negative, including the negative pole coating being made up of material with carbon element, binding agent and conductive agent;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on described carbon core surface, is coated on the second material with carbon element of described first carbon material surface; Described carbon core is graphite or MCMB; Described first material with carbon element is hard carbon, Graphene or CNT, and described second material with carbon element is amorphous carbon or graphite;
The porosity of described negative pole coating is 20%��40%, and the thickness of described negative pole coating is 40 ��m��90 ��m.
Preferably, the content of described carbon core is 59wt%��99.8wt%, and the content of described first material with carbon element is 0.1wt%��40wt%, and described second material with carbon element is 0.1wt%��10wt%.
Preferably, the content of described binding agent is the 0.5wt%��10wt% of described material with carbon element, binding agent and conductive agent total amount; The content of described conductive agent is the 0.5wt%��10wt% of described material with carbon element, binding agent and conductive agent total amount.
Preferably, the porosity of described negative pole coating is 25%��35%, and the thickness of described negative pole coating is 50 ��m��75 ��m.
The preparation method that present invention also provides a kind of lithium ion battery negative, comprises the following steps:
Material with carbon element, conductive agent are mixed with binding agent, obtains slurry;
Described slurry is coated on a current collector, obtains lithium ion battery negative;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on carbon core surface, is coated on the second material with carbon element of the first carbon material surface;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon;
The porosity of described lithium ion battery negative is 20%��40%, and the thickness of described lithium ion battery negative is 40 ��m��90 ��m.
Preferably, the preparation method of described material with carbon element comprises the following steps:
Carbon nuclear material, the first material with carbon element and the second material with carbon element are mixed in a solvent, obtains mixed liquor;
Described mixed liquor is evaporated, subsequently heat-treated, obtain material with carbon element;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
Preferably, the particle diameter of described carbon nuclear material is 10 ��m��30 ��m, and the particle diameter of described first material with carbon element is 0.1 ��m��10 ��m, and the particle diameter of described second material with carbon element is 0.1��10 ��m.
Preferably, the preparation method of described material with carbon element, comprise the following steps:
Carbon nuclear material, the first material with carbon element are mixed with solvent, obtains the first mixed liquor, the second material with carbon element is mixed with solvent, obtain the second mixed liquor;
By described first mixed liquor evaporation after-baking, obtain the first carbon coated material;
Described first carbon coated material is mixed with described second mixed liquor, evaporates after-baking, obtain material with carbon element;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
Preferably, it is petroleum base resin that described pyrolysis produces the material with carbon element presoma of hard carbon, and it is coal tar asphalt that described pyrolysis produces the material with carbon element presoma of amorphous carbon.
Preferably, obtain the process of slurry particularly as follows:
Mix with binding agent again after material with carbon element is mixed with conductive agent, obtain slurry.
This application provides a kind of lithium ion battery negative, it includes the negative pole coating being made up of material with carbon element, conductive agent and binding agent, wherein said material with carbon element includes carbon core, the first material with carbon element and the second material with carbon element, described first material with carbon element is coated on carbon core surface, described second material with carbon element is coated on described first carbon material surface, wherein said carbon core is graphite or MCMB, and described first material with carbon element is hard carbon, Graphene or CNT, and described second material with carbon element is amorphous carbon or graphite; The porosity of described negative pole coating is 20%��40%, and thickness is 40 ��m��90 ��m.
The coating of the lithium ion battery negative that the application provides is by material with carbon element, binding agent and conductive agent composition, wherein the carbon core of material with carbon element is to provide the component of energy density, first material with carbon element is to improve cell power density, the component of life-span and safety, and the second material with carbon element has relatively low specific surface area, it is prone to form solid phase electrode interface with electrolyte interface, to protect carbon core and the first material with carbon element, therefore the material with carbon element that the application provides is by arranging carbon core, first material with carbon element and the second material with carbon element, the negative pole that material with carbon element is applied to lithium ion battery is made to have higher energy density and power density, the material with carbon element that the application adopts simultaneously all can be obtained by simple approach, then the material with carbon element of the application is less costly, the application, also by the porosity of electrode characteristic parameter negative pole coating and the thickness that regulate lithium ion battery negative, makes lithium ion battery have higher energy density and power density further.
Detailed description of the invention
In order to be further appreciated by the present invention, below in conjunction with embodiment, the preferred embodiment of the invention is described, but it is to be understood that these describe simply as further illustrating the features and advantages of the present invention, rather than limiting to the claimed invention.
The embodiment of the invention discloses a kind of lithium ion battery negative, it is characterised in that include the negative pole coating being made up of material with carbon element, binding agent and conductive agent;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on described carbon core surface, is coated on the second material with carbon element of described first carbon material surface; Described carbon core is graphite or MCMB; Described first material with carbon element is hard carbon, Graphene or CNT, and described second material with carbon element is amorphous carbon or graphite;
The porosity of described negative pole coating is 20%��40%, and the thickness of described negative pole coating is 40 ��m��90 ��m.
This application provides a kind of lithium ion battery negative, the negative pole of described lithium ion battery includes the negative pole coating of collector and collection liquid surface. The coating of herein described lithium ion battery negative is made up of material with carbon element, binding agent and conductive agent. The application by introducing the material with carbon element of special construction in negative pole, and regulates the electrode characteristic parameter of negative material: the thickness of negative pole coating and porosity, makes the lithium ion battery of the application have higher energy density and power density.
Material with carbon element in the application negative pole coating has double-coating structure, wherein carbon core is the component of contribution energy density, it is coated with by the first material with carbon element, first material with carbon element is to have high power, the material of long-life and high security, it is that whole material improves power, the component of life-span and safety, first material with carbon element is coated with by the second material with carbon element, second material with carbon element has low specific surface area, easy and electrolyte interface forms Solid phase electrolysis interface, thus, carbon core and the first material with carbon element that the material with carbon element of the application is arranged make carbon electrode material have higher energy density, power density, life-span and safety, and be coated on the second material with carbon element and ensure that carbon electrode material and electrolyte interface form solid phase electrode interface, therefore the material with carbon element of the application is as the negative material of lithium ion battery, lithium ion battery is made to have higher energy density, power density, safety and life-span.
Herein described carbon core is graphite or MCMB, and described graphite can be native graphite, it is also possible to being Delanium, described carbon core is to provide the component of energy density in carbon electrode material. The content of described carbon core is 59wt%��99.8wt%, more preferably 70wt%��90wt%. If the content of carbon core is too low, then the energy density that can make carbon electrode material is too low, if the too high levels of carbon core, then can affect the lifting of material with carbon element power density. For the source of graphite or carbonaceous mesophase spherules, the application has no particular limits.
According to the application, the first material with carbon element being coated on carbon core surface is hard carbon, Graphene or CNT, described second material with carbon element is characterized by having high efficiency, long-life and high security, and it is the component improving power, life-span and safety in whole carbon electrode material. Described hard carbon refers to the carbon being difficult to be graphitized, and is the thermal decomposition product of high molecular polymer, and described hard carbon can be resin carbon, white carbon black etc. Described hard carbon material is respectively provided with significantly high reversible specific capacity. Described Graphene is the material of a kind of monolayer laminated structure having carbon atom to constitute. The content of described first material with carbon element is 0.1wt%��40wt%, it is preferred to 5wt%��35wt%, and the content of described first material with carbon element is too low, then can affect the lifting of power density, too high levels, then can cause that energy density declines. The application has no particular limits for the source of described hard carbon, Graphene or CNT. Material and the first material with carbon element being coated on carbon core surface herein as carbon core can not exchange, and this is owing to having high-power first material with carbon element as clad, being conducive to the quick charge of lithium ion to discharge.
The application is coated on the second material with carbon element of the first carbon material surface as external coating, it is possible to make it form solid phase electrode interface with electrolyte interface. Described second material with carbon element is amorphous carbon or graphite. The content of described second material with carbon element is 0.1wt%��10wt%, it is preferred to 3wt%��8wt%. The content of described second material with carbon element is too low, then can not be formed with electrolyte and be effectively protected interface, and too high levels then can make specific surface area cause that energy density declines too greatly.
The application makes lithium ion battery have higher energy density and power density also by regulating electrode characteristic, and wherein electrode characteristic includes porosity and the thickness of negative pole coating. The porosity of herein described negative pole coating is 20%��40%, and thickness is 40 ��m��90 ��m. Described porosity makes the power of electrode increase more than 40%, but energy density can be decreased obviously, and described porosity is preferably 25%��35%. The thickness of described negative pole coating is preferably 50 ��m��75 ��m, it is more preferably 55 ��m��70 ��m, the thickness of described negative pole coating is more than 90 ��m, then the energy density increase still power density of electrode is decreased obviously, and increases still energy density less than the power density of 40 ��m of electrodes and be decreased obviously.
According to the present invention, the performance of battery as electrode characteristic parameter, also can be impacted by the kind of described conductive agent and binding agent with addition. Described conductive agent is preferably one or both in white carbon black and graphite, and described binding agent is preferably Kynoar (PVDF) and carboxylic styrene butadiene latex (Letax). The content of described conductive agent is the 0.5wt%��10wt% of described material with carbon element, conductive agent and binding agent total amount, it is preferably 2wt%��8wt%, if content increases will cause that electrical conductivity increases still energy density and is decreased obviously, if the energy density of electrode can be made to increase for content reduction but electrical conductivity is decreased obviously. The content of described binding agent is the 0.5wt%��10wt% of described material with carbon element, conductive agent and binding agent total amount, it is preferred to 2wt%��8wt%, and the content of binding agent is excessive or the too small energy density that all can make electrode declines.
The lithium ion battery negative that the application provides is by selecting the material with carbon element of special construction, and regulates porosity and the thickness of electrode, makes lithium ion battery have higher power density and energy density.
The preparation method that present invention also provides lithium ion battery negative, comprises the following steps:
Material with carbon element, conductive agent are mixed with binding agent, obtains slurry;
Described slurry is coated on a current collector, obtains lithium ion battery negative;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on carbon core surface, is coated on the second material with carbon element of the first carbon material surface;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon;
The porosity of the coating of described lithium ion battery negative is 20%��40%, and the thickness of the coating of described lithium ion battery negative is 40 ��m��90 ��m.
The preparation method that the invention provides lithium ion battery negative, first it be prepared for the slurry of material with carbon element, conductive agent and binding agent, then is coated with on a current collector by slurry, namely obtains lithium ion battery negative.
The preparation method of herein described material with carbon element, it is preferable that be prepared according to following process:
Carbon nuclear material, the first material with carbon element and the second material with carbon element are mixed in a solvent, obtains mixed liquor;
Described mixed liquor is evaporated, subsequently heat-treated, obtain carbon electrode material;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
In the process preparing material with carbon element, the carbon nuclear material of the application, the first material with carbon element and the second material with carbon element, by mixing, evaporating and heat treated process, obtain the structure of double-layer carbon material cladding.
Carbon nuclear material, the first material with carbon element and the second material with carbon element, in the process preparing material with carbon element, are first mixed, obtain mixed liquor by the application in a solvent. In the process of described mixing, described solvent is preferably xylol, and it is conducive to the dissolving of above-mentioned three kinds of material with carbon elements, is also easy to separate in subsequent processes simultaneously. Described carbon nuclear material is graphite or MCMB, and its particle diameter is preferably 10��30 ��m, and the carbon nuclear material within the scope of this makes the energy density of material with carbon element the highest, and the particle diameter of described carbon nuclear material is more preferably 15��20 ��m. Described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, it is preferred to petroleum base resin, epoxy resin, natural plant fibre, lignin or carbon liquefied residue, more preferably petroleum base resin; The particle diameter of described first material with carbon element is preferably 0.1��10 ��m, and the first material with carbon element within the scope of this makes the power density of carbon electrode material the highest, and the particle diameter of described first material with carbon element is more preferably 2��7 ��m. Described second material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce amorphous carbon, it is preferably coal tar asphalt, the particle diameter of described second material with carbon element is preferably 0.1��10 ��m, the outer layer that the second material with carbon element within the scope of this is formed after making cladding is the most uniform, the most stable with the solid phase interface that electrolyte is formed, the particle diameter of described second material with carbon element is more preferably 3��8 ��m.
According to the present invention, after being prepared for mixed liquor, then described mixed liquor being evaporated, then carrying out heat treatment, thus obtaining material with carbon element. In order to make the organic solvent in mixed liquor be prone to steam, the application preferably employs Rotary Evaporators and described mixed liquor is evaporated. Described Rotary Evaporators is to pass through Electronic Control, make container under most suitable speed, disengagement area is increased with constant speed rotary, and make container for evaporation be in negative pressure state by vacuum pump, container for evaporation is concurrently placed in oil bath pan heated at constant temperature in rotation, and in bottle, solution is heated diffusive evaporation in rotary flask. The application in the process that mixed liquor is evaporated owing to the evaporation of solution makes the first material with carbon element and the second material with carbon element constantly precipitate out the surface being coated on carbon nuclear material. The temperature of described evaporation is preferably 100 DEG C��150 DEG C, and described evaporating temperature is too low, causes that the operating time is long, and the solution in described mixed liquor can not volatilize completely, affects the covered effect of carbon electrode material; Evaporating temperature is too high, then can cause that cladding is uneven. After being evaporated by described mixed liquor, then carry out heat treatment, make the material after pervaporation through dehydration, dehydrogenation polymerization and carbonization, ultimately form double-layer carbon material clad effectively. Affecting covered effect in order to avoid carbon electrode material introduces other impurity in preparation process, the application carries out under protecting preferably in nitrogen atmosphere. In order to ensure the covered effect of double-layer carbon material, described heat treated heating rate is preferably 2 DEG C/min��6 DEG C/min, and described heat treated temperature is preferably 800 DEG C��1200 DEG C, and the described heat treated time is preferably 1.5h��3h.
The preparation method of herein described material with carbon element can also carry out in the following manner:
Carbon nuclear material, the first material with carbon element are mixed with solvent, obtains the first mixed liquor, the second material with carbon element is mixed with solvent, obtain the second mixed liquor;
By described first mixed liquor evaporation after-baking, obtain the first carbon coated material;
Described first carbon coated material is mixed with described second mixed liquor, evaporates after-baking, obtain material with carbon element;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
The above-mentioned process preparing material with carbon element is first at Surface coating first material with carbon element of carbon nuclear material, again the solution of the first carbon coated material and the second material with carbon element is mixed, after pervaporation with heat treatment, finally it is coated with the second material with carbon element at the first carbon coated material surface, has obtained material with carbon element. By said process it can be seen that it is first be prepared for the material of the first material with carbon element carbon coated core that said process prepares the process of material with carbon element, then it is prepared for the double-coating material of cladding second layer material with carbon element again.
The method that the selection of parameter involved in the above-mentioned process preparing material with carbon element and preferred version prepare material with carbon element with the first is identical, no longer repeats herein.
According to the present invention, after prepared by described material with carbon element, then described material with carbon element, conductive agent are mixed with binding agent, obtain slurry. Described material with carbon element and conductive agent are pressed powders, it is easier to realize Homogeneous phase mixing, and binding agent is as full-bodied liquid, it is relatively difficult to realize with the Homogeneous phase mixing of pressed powder, therefore, the preparation process of described slurry is preferably: mixes with binding agent after being mixed with conductive agent by material with carbon element again, obtains slurry.
After obtaining slurry, described slurry is then coated by the application on a current collector, obtains lithium ion battery negative after drying.Wherein said collector is well known to those skilled in the art, and the application does not do special restriction, and the application can be preferably Copper Foil. In the process of coating, the application makes the porosity of negative pole coating be 20%��40% by the roller pitch of dancer rools press, and described roller pitch is 30 ��m��70 ��m.
This application provides a kind of lithium ion battery negative, it includes the negative pole coating being made up of material with carbon element, conductive agent and binding agent, wherein said material with carbon element includes carbon core, the first material with carbon element and the second material with carbon element, described first material with carbon element is coated on carbon core surface, described second material with carbon element is coated on described first carbon material surface, wherein said carbon core is graphite or MCMB, and described first material with carbon element is hard carbon, Graphene or CNT, and described second material with carbon element is amorphous carbon or graphite; The porosity of described negative pole coating is 20%��40%, and thickness is 40 ��m��90 ��m.
The coating of the lithium ion battery negative that the application provides is by material with carbon element, binding agent and conductive agent composition, wherein the carbon core of material with carbon element is to provide the component of energy density, first material with carbon element is to improve cell power density, the component of life-span and safety, and the second material with carbon element has relatively low specific surface area, it is prone to form solid phase electrode interface with electrolyte interface, to protect carbon core and the first material with carbon element, therefore the material with carbon element that the application provides is by arranging carbon core, first material with carbon element and the second material with carbon element, the negative pole that material with carbon element is applied to lithium ion battery is made to have higher energy density and power density, the material with carbon element that the application adopts simultaneously all can be obtained by simple approach, then the material with carbon element of the application is less costly, the application, also by the porosity of electrode characteristic parameter negative pole coating and the thickness that regulate lithium ion battery, makes lithium ion battery have higher energy density and power density further.
In order to be further appreciated by the present invention, below in conjunction with embodiment, carbon electrode material provided by the invention being described in detail, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Use the spherical natural graphite core as negative material of mean diameter 17 microns, namely material with carbon element A, the petroleum base resin using mean diameter 7 microns is coated with material as internal layer, namely material with carbon element B, uses the coal tar asphalt of mean diameter 3 microns as external sheath material.
First 800 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 200 grams of petroleum base resin are weighed respectively. Spherical natural graphite and solvent xylol are mixed to form the suspension that concentration is 0.5M; It is the solution of 1.0M that petroleum base resin and coal tar asphalt are added separately in solvent xylol form concentration. Three kinds of solution are at room temperature uniformly mixed; adopting Rotary Evaporators to dry at 125 DEG C makes solvent volatilize gradually; finally under nitrogen atmosphere is protected, in tube furnace, carry out heat treatment; nitrogen flow 30ml/min; 5 DEG C/min of heating rate; final temperature 1000 DEG C, stops 2h, obtains the advanced material with carbon element of double-coating.
Prepared material with carbon element 900g and 50g white carbon black is mixed 20min in Dry powder mixing apparatus, adds the PVDF/NMP solution of 500g10%, planetary-type mixer mixes 30min, the slurry obtained coating on Copper Foil, dry, and adopt roll squeezer pair roller, obtain lithium ion battery negative; In pair roller process, the roller pitch of roll squeezer is 50 ��m, and the porosity of lithium ion battery negative coating is 31%, and thickness is 79 ��m.The negative pole prepared by the present embodiment is as the negative pole of half-cell, and the test result of half-cell performance is as shown in table 1.
Embodiment 2
Use the spherical natural graphite core as negative material of mean diameter 17 microns, namely material with carbon element A, the lignin using mean diameter 7 microns is coated with material as internal layer, namely material with carbon element B, uses the coal tar asphalt of mean diameter 3 microns as external sheath material.
First 800 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 200 grams of lignins are weighed respectively. Spherical natural graphite and solvent xylol are mixed to form the suspension that concentration is 0.5M. It is the solution of 1.0M that lignin and coal tar asphalt are added separately in solvent xylol form concentration. First lignin liquor and graphite suspension are at room temperature uniformly mixed, adopting Rotary Evaporators to dry at 125 DEG C makes solvent volatilize gradually, finally under nitrogen atmosphere is protected, in tube furnace, carry out heat treatment, nitrogen flow 30ml/min, 5 DEG C/min of heating rate, final temperature 1000 DEG C, stops 2h, obtains the material of one layer of cladding; Then it is coated with material this layer and joins mix homogeneously formation suspension in cold primer-oil; adopting Rotary Evaporators to dry at 125 DEG C makes solvent volatilize gradually; finally under nitrogen atmosphere is protected, in tube furnace, carry out heat treatment; nitrogen flow 30ml/min; 5 DEG C/min of heating rate; final temperature 1000 DEG C, stops 2h, obtains the advanced material with carbon element of double-coating.
Prepared material with carbon element 895g and 52.5g white carbon black is mixed 20min in Dry powder mixing apparatus, add the PVDF/NMP solution of 525g10%, planetary-type mixer mixes 30min, the slurry obtained coating on Copper Foil, dry, and adopt roll squeezer pair roller, obtain lithium ion battery negative; In pair roller process, the roller pitch of roll squeezer is 70 ��m, and the porosity of lithium ion battery negative coating is 40%, and thickness is 90 ��m. The negative pole prepared by the present embodiment is as the negative pole of half-cell, and the test result of half-cell performance is as shown in table 1.
Embodiment 3
Use the spherical natural graphite core as negative material of mean diameter 17 microns, namely material with carbon element A, the petroleum base resin using mean diameter 7 microns is coated with material as internal layer, namely material with carbon element B, uses the coal tar asphalt of mean diameter 3 microns as external sheath material.
First 500 grams of spherical natural graphites, 200 grams of coal tar asphaltes, 800 grams of petroleum base resin are weighed respectively. Spherical natural graphite and solvent xylol are mixed to form the suspension that concentration is 0.5M, and it is the solution of 1.0M that resin and Colophonium are added separately in solvent xylol form concentration. Three kinds of solution are at room temperature uniformly mixed; adopting Rotary Evaporators to dry at 125 DEG C makes solvent volatilize gradually; finally under nitrogen atmosphere is protected, in tube furnace, carry out heat treatment; nitrogen flow 30ml/min; 5 DEG C/min of heating rate; final temperature 1000 DEG C, stops 2h, obtains the advanced material with carbon element of double-coating.
Prepared material with carbon element 980g and 10g white carbon black is mixed 20min in Dry powder mixing apparatus, adds the PVDF/NMP solution of 100g10%, planetary-type mixer mixes 30min, the slurry obtained coating on Copper Foil, dry, and adopt roll squeezer pair roller, obtain lithium ion battery negative; In pair roller process, the roller pitch of roll squeezer is 30 ��m, and the porosity of lithium ion battery negative coating is 20%, and thickness is 40 ��m.The negative pole prepared by the present embodiment is as the negative pole of half-cell, and the test result of half-cell performance is as shown in table 1.
The material with carbon element of table 1 embodiment 1��3 preparation is as the performance data table of electrode material half-cell
The explanation of above example is only intended to help to understand method and the core concept thereof of the present invention. It should be pointed out that, for those skilled in the art, under the premise without departing from the principles of the invention, it is also possible to the present invention carries out some improvement and modification, these improve and modify in the protection domain also falling into the claims in the present invention.
Described above to the disclosed embodiments, makes professional and technical personnel in the field be capable of or uses the present invention. The multiple amendment of these embodiments be will be apparent from for those skilled in the art, and generic principles defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments. Therefore, the present invention is not intended to be limited to the embodiments shown herein, and is to fit to the widest scope consistent with principles disclosed herein and features of novelty.
Claims (10)
1. a lithium ion battery negative, it is characterised in that include the negative pole coating being made up of material with carbon element, binding agent and conductive agent;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on described carbon core surface, is coated on the second material with carbon element of described first carbon material surface; Described carbon core is graphite or MCMB; Described first material with carbon element is hard carbon, Graphene or CNT, and described second material with carbon element is amorphous carbon or graphite;
The porosity of described negative pole coating is 20%��40%, and the thickness of described negative pole coating is 40 ��m��90 ��m.
2. lithium ion battery negative according to claim 1, it is characterised in that the content of described carbon core is 59wt%��99.8wt%, the content of described first material with carbon element is 0.1wt%��40wt%, and described second material with carbon element is 0.1wt%��10wt%.
3. lithium ion battery negative according to claim 1, it is characterised in that the content of described binding agent is the 0.5wt%��10wt% of described material with carbon element, binding agent and conductive agent total amount; The content of described conductive agent is the 0.5wt%��10wt% of described material with carbon element, binding agent and conductive agent total amount.
4. lithium ion battery negative according to claim 1, it is characterised in that the porosity of described negative pole coating is 25%��35%, the thickness of described negative pole coating is 50 ��m��75 ��m.
5. a preparation method for lithium ion battery negative, comprises the following steps:
Material with carbon element, conductive agent are mixed with binding agent, obtains slurry;
Described slurry is coated on a current collector, obtains lithium ion battery negative;
Described material with carbon element includes: carbon core, is coated on first material with carbon element on carbon core surface, is coated on the second material with carbon element of the first carbon material surface;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon;
The porosity of described lithium ion battery negative is 20%��40%, and the thickness of described lithium ion battery negative is 40 ��m��90 ��m.
6. preparation method according to claim 5, it is characterised in that the preparation method of described material with carbon element comprises the following steps:
Carbon nuclear material, the first material with carbon element and the second material with carbon element are mixed in a solvent, obtains mixed liquor;
Described mixed liquor is evaporated, subsequently heat-treated, obtain material with carbon element;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
7. the preparation method according to claim 5 or 6, it is characterised in that the particle diameter of described carbon nuclear material is 10 ��m��30 ��m, the particle diameter of described first material with carbon element is 0.1 ��m��10 ��m, and the particle diameter of described second material with carbon element is 0.1��10 ��m.
8. preparation method according to claim 5, it is characterised in that the preparation method of described material with carbon element, comprises the following steps:
Carbon nuclear material, the first material with carbon element are mixed with solvent, obtains the first mixed liquor, the second material with carbon element is mixed with solvent, obtain the second mixed liquor;
By described first mixed liquor evaporation after-baking, obtain the first carbon coated material;
Described first carbon coated material is mixed with described second mixed liquor, evaporates after-baking, obtain material with carbon element;
Described carbon nuclear material is graphite or MCMB, and described first material with carbon element is the material with carbon element presoma that Graphene, CNT or pyrolysis produce hard carbon, and described second material with carbon element is the material with carbon element presoma that graphite or pyrolysis produce amorphous carbon.
9. preparation method according to claim 8, it is characterised in that it is petroleum base resin that described pyrolysis produces the material with carbon element presoma of hard carbon, it is coal tar asphalt that described pyrolysis produces the material with carbon element presoma of amorphous carbon.
10. preparation method according to claim 5, it is characterised in that obtain the process of slurry particularly as follows:
Mix with binding agent again after material with carbon element is mixed with conductive agent, obtain slurry.
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