CN107394138A - Lithium ion battery negative material structure, lithium ion battery and preparation method thereof - Google Patents

Lithium ion battery negative material structure, lithium ion battery and preparation method thereof Download PDF

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Publication number
CN107394138A
CN107394138A CN201710537938.0A CN201710537938A CN107394138A CN 107394138 A CN107394138 A CN 107394138A CN 201710537938 A CN201710537938 A CN 201710537938A CN 107394138 A CN107394138 A CN 107394138A
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lithium ion
ion battery
preparation
battery negative
negative material
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CN107394138B (en
Inventor
方小红
尤莹
万吉祥
徐麟
徐一麟
陈小源
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Pylon Technologies Co Ltd
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Shanghai Advanced Research Institute of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The present invention provides a kind of lithium ion battery negative material structure, lithium ion battery and preparation method thereof, and the preparation method comprises the following steps：1）Silicon nano material, carbon nanomaterial and additive are placed in organic solvent and make dispersion liquid；2）Metal catalytic substrate is provided, by the dispersion in the upper surface of the metal catalytic substrate；3）In step 2）The upper surface of obtained structure forms graphene film.The cell negative electrode material structure of the present invention not only remains the inherent characteristic of silicium cathode material and graphene, can also play cooperative effect between the two；Simultaneously, effectively contacting between silicon nano material/carbon nanomaterial laminated film and metal catalytic substrate collector can be achieved, efficient storage lithium ability can be not only provided, also silicon nano material Volume Changes larger in charge and discharge process are alleviated, the generation for effectively suppressing and improving negative material internal stress avoids negative material efflorescence.

Description

Lithium ion battery negative material structure, lithium ion battery and preparation method thereof
Technical field
The invention belongs to material processing technology of preparing field, more particularly to a kind of lithium ion battery negative material structure, Lithium ion battery and preparation method thereof.
Background technology
First generation lithium ion battery is successfully developed from Sony corporation of Japan, because its energy density is high, is had extended cycle life And environmental pollution it is small many advantages, such as made it the preferred battery that most of portable electric appts are favored.Lithium ion Battery is made up of positive pole, negative pole, electrolyte and barrier film.Under normal circumstances, the positive pole of lithium ion by the metallic compound containing lithium (such as Cobalt acid lithium (LiCoO2), LiFePO4 (LiFePO4) and LiMn2O4 (LiMn2O4) form.And negative pole is by that can store lithium ion Material composition, such as carbon, transition metal and other alloy materials (such as silicon, germanium).The selection of negative material is to lithium ion battery Chemical property and cyclical stability all there is large effect.Although graphite is widely used in negative electrode of lithium ion battery material Material, but because the shortcomings of its relatively low theoretical specific capacity and charging and discharging capabilities difference limits lithium ion battery storage lithium performance Lifting.In order to improve the energy density of lithium ion battery and storage lithium ability, scientific research personnel constantly explores and is more applicable for lithium The material of ion battery negative pole, to develop higher quality and the good lithium ion battery of security.
Theoretical specific capacity and preferable operating voltage of the silicon due to its superelevation, it is considered as most promising to make it One of negative material.It is exactly the material bodies in de--process of intercalation repeatedly but silicon also has inferior position as negative electrode of lithium ion battery Big change occurs for product, and electrode interior produces larger stress, makes negative material efflorescence cause structure to destroy, electrochemistry cyclicity Can be poor.Simultaneously as the change of silicon electrode volume so that the solid electrolyte interface film (SEI) that electrode surface is formed is constantly broken Split, cause it to lose the function of preventing organic solvent molecule from entering in electrode material.Moreover, exposed electrode surface meeting again Reacted with electrolyte to form new SEI films, so cause the thickness of SEI films to be continuously increased repeatedly and ultimately result in storage lithium performance Significantly decay, seriously limit application and development of the silicon in lithium ion battery.
The content of the invention
In view of the above the shortcomings that prior art, it is an object of the invention to provide a kind of lithium ion battery negative material Structure, lithium ion battery and preparation method thereof, exist for solving graphite of the prior art as negative electrode of lithium ion battery The problem of theoretical specific capacity is low, charging and discharging capabilities are poor, and silicon is existing as negative electrode of lithium ion battery refers to that change is big, follows The problem of ring stability difference.
In order to achieve the above objects and other related objects, the present invention provides a kind of system of lithium ion battery negative material structure Preparation Method, the preparation method comprise the following steps：
1) silicon nano material, carbon nanomaterial and additive are placed in organic solvent and make dispersion liquid；
2) metal catalytic substrate is provided, by the dispersion in the upper surface of the metal catalytic substrate；
3) upper surface of the structure obtained in step 2) forms graphene film.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 1), The silicon nano material includes at least one of nano silicon particles, silicon nanowires or silicon nanofiber.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 1), The carbon nanomaterial includes at least one of CNT, carbon nano-fiber, graphene powder or fullerene.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 1), The additive includes at least one of conductive additive, stabilizer and binding agent.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, the conduction adds Agent is added to include at least one of acetylene black or graphite.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 1), The organic solvent includes at least one of 1-METHYLPYRROLIDONE, ethanol or isopropanol.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 1), The concentration of silicon nano material described in the dispersion liquid is 3mg/ml~300mg/ml；Carbon nanomaterial described in the dispersion liquid Concentration be 0.1mg/ml~30mg/ml.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 2), The material of the metal catalytic substrate is gold, platinum, palladium, iridium, ruthenium, nickel, one kind in copper or at least two alloy material or tool There are other metal foil substrate materials of the above coat of metal or alloy layer.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 2), The dispersion is also included carrying out the metal catalytic substrate clearly before the upper surface of the metal catalytic substrate Wash and the step of polishing.
As the present invention lithium ion battery negative material structure preparation method a kind of preferred scheme, using acetic acid, Nitric acid or hydrochloric acid carry out chemical polishing to the metal catalytic substrate or the metal catalytic substrate are carried out under the conditions of phosphoric acid Electrochemical polish.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, in step 2), Using any of Best-Effort request, spin coating, scraper, spraying, wet coating, silk-screen printing, roller coating or board-like coating by described in Dispersion is in the upper surface of the metal catalytic substrate.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 2) and step It is rapid 3) between the structure that also includes obtaining step 2) carry out heat treatment step, the dispersion liquid of coating is solidified.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 2) is obtained To structure be placed in reducing atmosphere and be heated to reaction temperature, and be passed through carbon-source gas into the reducing atmosphere with step 2) The upper surface of obtained structure forms the graphene film.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 2) is obtained To structure be placed in reducing atmosphere and be heated to reaction temperature, and be passed through carbon-source gas into the reducing atmosphere with step 2) The upper surface of obtained structure forms the graphene film and specifically comprised the following steps：
3-1) structure for obtaining step 2) is placed in tube furnace；
Reducibility gas 3-2) is passed through into the tube furnace, the structure that step 2) is obtained is heated to the reaction temperature Insulation, and carbon-source gas are passed through into the tube furnace in insulating process, with the upper surface shape of the structure obtained in step 2) Into the graphene film.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 3-1) with Step 3-2) between also include the step of being cleaned to reducibility gas pipeline.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 3-2) In, the reducibility gas that is passed through into the tube furnace includes hydrogen, the mixed gas of hydrogen and nitrogen or hydrogen and argon gas Mixed gas.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 3-2) In, the carbon-source gas being passed through into the tube furnace include at least one of methane, ethene, acetylene, ethanol or hexamethylene.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 3-2) In, the reaction temperature is 500 DEG C~1000 DEG C.
As a kind of preferred scheme of the preparation method of the lithium ion battery negative material structure of the present invention, step 3-2) In, soaking time is 5min~30min.
The present invention also provides a kind of lithium ion battery negative material structure, the lithium ion battery negative material structure bag Include：
Metal catalytic substrate；
Curing material layer, positioned at the upper surface of the metal catalytic substrate；The curing material layer is to include silicon nanometer material The composite layer of material, carbon nanomaterial and additive；
Graphene film, positioned at the upper surface of the curing material layer.
As a kind of preferred scheme of the lithium ion battery negative material structure of the present invention, the material of the metal catalytic substrate Expect for one kind in gold, platinum, palladium, iridium, ruthenium, nickel, copper or at least two alloy material or there is the above coat of metal or alloy Other metal foil substrate materials of coating.
As a kind of preferred scheme of the lithium ion battery negative material structure of the present invention, the silicon nano material includes silicon At least one of nano particle, silicon nanowires or silicon nanofiber.
As a kind of preferred scheme of the lithium ion battery negative material structure of the present invention, the carbon nanomaterial includes carbon At least one of nanotube, carbon nano-fiber, graphene powder or fullerene.
As a kind of preferred scheme of the lithium ion battery negative material structure of the present invention, the additive adds including conduction Add at least one of agent, binding agent and stabilizer.
As a kind of preferred scheme of the lithium ion battery negative material structure of the present invention, the conductive additive includes second At least one of acetylene black or graphite.
The present invention also provides a kind of negative electrode of lithium ion battery, and the negative electrode of lithium ion battery is included as in above-mentioned either a program Described lithium ion battery negative material structure.
The present invention also provides a kind of lithium ion battery, and the lithium ion battery includes the lithium ion as described in above-mentioned scheme GND.
As described above, the lithium ion battery negative material structure of the present invention, lithium ion battery and preparation method thereof, have with Lower beneficial effect：By being used as active material from silicon nano material in preparation process, carbon nanomaterial is used as and led the present invention Electric additive and dispersant, being prepared using chemical vapour deposition technique can be directly multiple coated with silicon nano material/carbon nanomaterial The metal catalytic substrate surface for closing film grows graphene film so as to form composite negative pole material, not only remains silicium cathode material The inherent characteristic of material and graphene, while cooperative effect between the two is played, application value is more extensive；Meanwhile it can be achieved Effectively contacting between silicon nano material/carbon nanomaterial laminated film and metal catalytic substrate collector, can not only provide Efficient storage lithium ability, while graphene film is flexible mesh substrate, also alleviates silicon nano material in charge and discharge process Larger Volume Changes, the generation for effectively suppressing and improving negative material internal stress avoids negative material efflorescence, and prepares work Skill is simple, is advantageous to industrialized production, can also be effectively improved the electrochemical stability and performance of lithium ion battery.
Brief description of the drawings
Fig. 1 is shown as the flow of the preparation method of the lithium ion battery negative material structure provided in the embodiment of the present invention one Figure.
Fig. 2 to Fig. 4 is shown as the preparation method of the lithium ion battery negative material structure provided in the embodiment of the present invention one Structural representation in each step.
Prepared by the preparation method that Fig. 5 is shown as the lithium ion battery negative material structure provided in the embodiment of the present invention one Lithium ion battery negative material structure is used for the cyclic voltammetry figure of negative electrode of lithium ion battery.
Component label instructions
1 metal catalytic substrate
2 curing material layers
3 graphene films
Embodiment
Illustrate embodiments of the present invention below by way of specific instantiation, those skilled in the art can be by this specification Disclosed content understands other advantages and effect of the present invention easily.The present invention can also pass through specific realities different in addition The mode of applying is embodied or practiced, the various details in this specification can also be based on different viewpoints with application, without departing from Various modifications or alterations are carried out under the spirit of the present invention.
Fig. 1 is referred to Fig. 5.It should be noted that the diagram provided in the present embodiment only illustrates this in a schematic way The basic conception of invention, though only showing the component relevant with the present invention in diagram rather than according to package count during actual implement Mesh, shape and size are drawn, and form, quantity and the ratio of each component can be a kind of random change during its actual implementation, and its Assembly layout form may also be increasingly complex.
Embodiment one
Referring to Fig. 1, the present invention provides a kind of preparation method of lithium ion battery negative material structure, the lithium-ion electric The preparation method of pond negative material structure comprises the following steps：
1) silicon nano material, carbon nanomaterial and additive are placed in organic solvent and make dispersion liquid；
2) metal catalytic substrate is provided, by the dispersion in the upper surface of the metal catalytic substrate；
3) upper surface of the structure obtained in step 2) forms graphene film.
In step 1), the S1 steps in Fig. 1 are referred to, silicon nano material, carbon nanomaterial and additive have been placed in Dispersion liquid is made in solvent.
As an example, the silicon nano material can be included in nano silicon particles, silicon nanowires or silicon nanofiber extremely Few one kind, i.e., described silicon nano material can be nano silicon particles, silicon nanowires or silicon nanofiber, or silicon nanometer Any two or three of mixture in grain, silicon nanowires or silicon nanofiber.Preferably, in the present embodiment, the silicon nanometer Material is nano silicon particles.
As an example, the size of the silicon nano material can be set according to being actually needed, it is preferable that the present embodiment In, the particle diameter of the silicon nano material is 15nm~300nm.
As an example, the carbon nanomaterial is included in CNT, carbon nano-fiber, graphene powder or fullerene At least one, i.e., described carbon nanomaterial can be CNT, carbon nano-fiber, graphene powder or fullerene, can also For any two kinds, three kinds or four kinds in CNT, carbon nano-fiber, graphene powder or fullerene of mixture.Preferably, In the present embodiment, the carbon nanomaterial is CNT.
As an example, the additive can include at least one of conductive additive, stabilizer and binding agent, preferably Ground, the conductive additive include at least one of acetylene black or graphite, i.e., described conductive additive can be acetylene black or Graphite, or the mixture of acetylene black and graphite.
As an example, the organic solvent can include at least one of 1-METHYLPYRROLIDONE, ethanol or isopropanol. Preferably, in the present embodiment, the organic solvent is 1-METHYLPYRROLIDONE.
As an example, the silicon nano material, the carbon nanomaterial and the additive can be carried out with arbitrary proportion Mixed dissolution is in the organic solvent, with the dispersion liquid of concentration needed for preparation, it is preferable that in the present embodiment, the dispersion liquid Described in the concentration of silicon nano material be 3mg/ml~300mg/ml；The concentration of carbon nanomaterial is described in the dispersion liquid 0.1mg/ml~30mg/ml.
In step 2), S2 steps and Fig. 2 to Fig. 3 in Fig. 1 are referred to, there is provided metal catalytic substrate 1, will be described scattered Liquid is coated on the upper surface of the metal catalytic substrate 1.
As an example, provide the metal catalytic substrate 1, as shown in Fig. 2 the material of the metal catalytic substrate 1 can be with For one kind in gold, platinum, palladium, iridium, ruthenium, nickel, copper or at least two alloy material or there is the above coat of metal or Alloy Plating Other metal foil substrate materials of layer；Preferably, in the present embodiment, the metal catalytic substrate 1 is copper foil substrate.
As an example, the dispersion is also included by described in before the upper surface of the metal catalytic substrate 1 Metal catalytic substrate 1 is cleaned and the step of polishing.
Cleaned as an example, the metal catalytic substrate 1 can be placed in deionized water or organic solvent, preferably Ground, in the present embodiment, the metal catalytic substrate 1 is respectively placed in acetone and ethanol and is cleaned by ultrasonic
As an example, chemical polishing is carried out or in phosphoric acid bar to the metal catalytic substrate 1 using acetic acid, nitric acid or hydrochloric acid Electrochemical polish is carried out to the metal catalytic substrate 1 under part, it is preferable that in the present embodiment, the metal after cleaning is urged Change substrate 1 and be placed in orthophosphoric acid solution the electrochemical polish under 5V voltage conditions.Electrochemistry is carried out to the metal catalytic substrate 1 The time of polishing can be set according to being actually needed, it is preferable that in the present embodiment, the metal catalytic substrate 1 is carried out The time of electrochemical polish can be 5min~15min.
As an example, after the metal catalytic substrate 1 is polished, in addition to the metal catalytic after cleaning polishing served as a contrast The deionized water rinsed clean of bottom 1, and dried up with nitrogen.
As an example, Best-Effort request, spin coating, scraper, spraying, wet coating, silk-screen printing, roller coating or board-like can be used Any of coating is by the dispersion in the upper surface of the metal catalytic substrate 1.Preferably, in the present embodiment, Using spin coating proceeding by the dispersion in the upper surface of the metal catalytic substrate 1.
As an example, the structure for also including obtaining step 2) between step 2) and step 3) carries out heat treatment step, with The dispersion liquid of coating is solidified, to obtain curing material layer 2, as shown in Figure 3.
In step, 3) in, S3 steps and Fig. 4 in Fig. 1 are referred to, stone is formed in the upper surface for the structure that step 2) obtains Black alkene film 3.
As an example, the structure that step 2) is obtained is placed in reducing atmosphere and is heated to reaction temperature, and to the reduction Carbon-source gas are passed through in atmosphere the graphene film 3 is formed with the upper surface of the structure obtained in step 2).
Specifically, the structure that step 2) is obtained is placed in reducing atmosphere and is heated to reaction temperature, and Primordial Qi is gone back to described Carbon-source gas are passed through in atmosphere the graphene film 3 is formed with the upper surface of the structure obtained in step 2) and specifically include following step Suddenly：
3-1) structure for obtaining step 2) is placed in tube furnace；
Reducibility gas 3-2) is passed through into the tube furnace, the structure that step 2) is obtained is heated to the reaction temperature Insulation, and carbon-source gas are passed through into the tube furnace in insulating process, with the upper surface shape of the structure obtained in step 2) Into the graphene film 3.
As an example, step 3-1) and step 3-2) between also include the step of being cleaned to reducibility gas pipeline.
As an example, step 3-2) in, the reducibility gas being passed through into the tube furnace includes hydrogen, hydrogen and nitrogen Mixed gas or the mixed gas of hydrogen and argon gas.Preferably, in the present embodiment, the reducibility gas is hydrogen.
As an example, step 3-2) in, the carbon-source gas being passed through into the tube furnace include methane, ethene, acetylene, second At least one of alcohol or hexamethylene, i.e., the carbon-source gas being passed through into the tube furnace can be methane, ethene, acetylene, second Alcohol or hexamethylene, or any mixed gas of two or more in methane, ethene, acetylene, ethanol or hexamethylene.It is preferred that Ground, in the present embodiment, the carbon-source gas are methane.
As an example, step 3-2) in, the reaction temperature is 500 DEG C~1000 DEG C, i.e., the structure obtained step 2) The temperature being heated to is 500 DEG C~1000 DEG C.
As an example, step 3-2) in, soaking time is 5min~30min.
Specifically, in one example, the metal catalytic substrate for being coated with the dispersion liquid is placed in tubular type furnace system, clearly Wash after reducibility gas transfer pipeline, air pressure in the tube furnace be evacuated to below 5Pa with mechanical pump, be passed through hydrogen and It is incubated at 1000 DEG C, methane carbon source is passed through in insulating process.
Please continue to refer to Fig. 3, the present invention also provides a kind of lithium ion battery negative material structure, and the lithium ion battery is born Pole material structure uses above-mentioned preparation method in the present embodiment to be prepared, the lithium ion battery negative material structure bag Include：Metal catalytic substrate 1；Curing material layer 2, the curing material layer 2 are located at the upper surface of the metal catalytic substrate 1；Institute It is the composite layer for including silicon nano material, carbon nanomaterial and additive to state curing material layer 2；Graphene film 3, it is described Graphene film is located at the upper surface of the curing material layer 2.
As an example, the material of the metal catalytic substrate 1 can be gold, platinum, palladium, iridium, ruthenium, nickel, one kind in copper or At least two alloy material or other metal foil substrate materials with the above coat of metal or alloy layer；Preferably, originally Embodiment China, the metal catalytic substrate 1 is copper foil substrate.
As an example, the silicon nano material can be included in nano silicon particles, silicon nanowires or silicon nanofiber extremely Few one kind, i.e., described silicon nano material can be nano silicon particles, silicon nanowires or silicon nanofiber, or silicon nanometer Any two or three of mixture in grain, silicon nanowires or silicon nanofiber.Preferably, in the present embodiment, the silicon nanometer Material is nano silicon particles.
As an example, the carbon nanomaterial is included in CNT, carbon nano-fiber, graphene powder or fullerene At least one, i.e., described carbon nanomaterial can be CNT, carbon nano-fiber, graphene powder or fullerene, can also For any two kinds, three kinds or four kinds in CNT, carbon nano-fiber, graphene powder or fullerene of mixture.Preferably, In the present embodiment, the carbon nanomaterial is CNT.
As an example, the additive can include at least one of conductive additive, binding agent and stabilizer, preferably Ground, the conductive additive include at least one of acetylene black or graphite, i.e., described conductive additive can be acetylene black or Graphite, or the mixture of acetylene black and graphite.
Compared to the silicon of bulky grain size, silicon nano material has higher cyclical stability and reversible capacity；And carbon is received Rice material has excellent electricity and mechanical property concurrently, compound by the way that silicon nano material is carried out with carbon nanomaterial, can be by carbon The structural advantage of nano material and the storage lithium ability of silicon nano material are combined to prepare the negative material structure of lithium ion battery； Carbon nanomaterial can buffer the volumetric expansion that silicon nano material occurs in cyclic process, be effectively improved between silicon nano material Agglomeration, increase the electric conductivity of material；And silicon nano material can be significantly increased due to the storage lithium specific capacity of itself The circulation specific capacity of lithium ion battery so that the storage lithium ability of lithium ion battery is significantly improved.
By being used as active material from silicon nano material in preparation process, carbon nanomaterial adds the present invention as conduction Add agent and dispersant, being prepared using chemical vapour deposition technique can be directly coated with silicon nano material/carbon nanomaterial THIN COMPOSITE The metal catalytic substrate surface of film grows graphene film so as to form composite negative pole material, not only remain silicium cathode material and The inherent characteristic of graphene, can also play cooperative effect between the two, and application value is more extensive；Meanwhile achievable silicon is received Effectively contacting between rice material/carbon nanomaterial laminated film and metal catalytic substrate collector, can not only provide efficiently Storage lithium ability, while graphene film is flexible mesh substrate, and it is larger in charge and discharge process also to alleviate silicon nano material Volume Changes, the generation for effectively suppressing and improving negative material internal stress avoids negative material efflorescence, and preparation technology letter It is single, be advantageous to industrialized production, can also be effectively improved the electrochemical stability and performance of lithium ion battery.
Fig. 5 is negative electrode of lithium ion battery material prepared by the preparation method of lithium ion battery negative material structure in the present embodiment Expect that structure is used for the volt-ampere test chart that negative electrode of lithium ion battery circulates 6 times, as shown in Figure 5, in discharge process first, electrode meeting There is an obvious discharge peak, and can be disappeared in subsequent circulation, it corresponds to the irreversible decomposable process of electrolyte And the formation of solid electrolyte interface；Since circulating 2 times, the Cyclic voltamogram curves of two electrodes is in shape almost Substantially it is consistent, shows to have tended to form stable solid electrolyte interface in electrode surface and there is metastable knot Structure, and good reversibility.
Embodiment two
The present invention also provides a kind of negative electrode of lithium ion battery, and the negative electrode of lithium ion battery is included as described in embodiment one Lithium ion battery negative material structure.
Embodiment three
The present invention also provides a kind of lithium ion battery, and the lithium ion battery includes the lithium ion as described in embodiment two GND.
In summary, the present invention provides a kind of lithium ion battery negative material structure, lithium ion battery and preparation method thereof, The preparation method comprises the following steps：1) silicon nano material, carbon nanomaterial and additive are placed in organic solvent and prepared Go out dispersion liquid；2) metal catalytic substrate is provided, by the dispersion in the upper surface of the metal catalytic substrate；3) in step The upper surface of the rapid structure 2) obtained forms graphene film.The present invention in preparation process from silicon nano material by being used as Active material, carbon nanomaterial are prepared using chemical vapour deposition technique and can directly coated as conductive additive and dispersant The metal catalytic substrate surface for having silicon nano material/carbon nanomaterial laminated film grows graphene film so as to form Compound Negative Pole material, the inherent characteristic of silicium cathode material and graphene is not only remained, can also play cooperative effect between the two, applied Value is more extensive；Meanwhile it can be achieved between silicon nano material/carbon nanomaterial laminated film and metal catalytic substrate collector Effective contact, can not only provide efficient storage lithium ability, while graphene film is flexible mesh substrate, also alleviates silicon Nano material Volume Changes larger in charge and discharge process, the generation for effectively suppressing and improving negative material internal stress avoid Negative material efflorescence, and preparation technology is simple, is advantageous to industrialized production, can also be effectively improved the electrochemistry of lithium ion battery Stability and performance.
The above-described embodiments merely illustrate the principles and effects of the present invention, not for the limitation present invention.It is any ripe Know the personage of this technology all can carry out modifications and changes under the spirit and scope without prejudice to the present invention to above-described embodiment.Cause This, those of ordinary skill in the art is complete without departing from disclosed spirit and institute under technological thought such as Into all equivalent modifications or change, should by the present invention claim be covered.

Claims (27)

1. a kind of preparation method of lithium ion battery negative material structure, it is characterised in that the preparation method includes following step Suddenly：
1) silicon nano material, carbon nanomaterial and additive are placed in organic solvent and make dispersion liquid；
2) metal catalytic substrate is provided, by the dispersion in the upper surface of the metal catalytic substrate；
3) upper surface of the structure obtained in step 2) forms graphene film.
2. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 1) In, the silicon nano material includes at least one of nano silicon particles, silicon nanowires or silicon nanofiber.
3. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 1) In, the carbon nanomaterial includes at least one of CNT, carbon nano-fiber, graphene powder or fullerene.
4. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 1) In, the additive includes at least one of conductive additive, stabilizer and binding agent.
5. the preparation method of lithium ion battery negative material structure according to claim 4, it is characterised in that：The conduction Additive includes at least one of acetylene black or graphite.
6. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 1) In, the organic solvent includes at least one of 1-METHYLPYRROLIDONE, ethanol or isopropanol.
7. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 1) In, the concentration of silicon nano material described in the dispersion liquid is 3mg/ml~300mg/ml；Carbon nanometer described in the dispersion liquid The concentration of material is 0.1mg/ml~30mg/ml.
8. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 2) In, the material of the metal catalytic substrate is gold, platinum, palladium, iridium, ruthenium, nickel, one kind in copper or at least two alloy material, Or other metal foil substrate materials with the above coat of metal or alloy layer.
9. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 2) In, the dispersion is also included carrying out the metal catalytic substrate before the upper surface of the metal catalytic substrate The step of cleaning and polishing.
10. the preparation method of lithium ion battery negative material structure according to claim 8, it is characterised in that：Using vinegar Acid, nitric acid or hydrochloric acid carry out chemical polishing to the metal catalytic substrate or the metal catalytic substrate are entered under the conditions of phosphoric acid Row electrochemical polish.
11. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 2) In, using any of Best-Effort request, spin coating, scraper, spraying, wet coating, silk-screen printing, roller coating or board-like coating by institute Dispersion is stated in the upper surface of the metal catalytic substrate.
12. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：Step 2) Structure with also including obtaining step 2) between step 3) carries out heat treatment step, and the dispersion liquid of coating is consolidated Change.
13. the preparation method of lithium ion battery negative material structure according to claim 1, it is characterised in that：By step 2) structure obtained, which is placed in reducing atmosphere, is heated to reaction temperature, and is passed through carbon-source gas into the reducing atmosphere with step The upper surface of the rapid structure 2) obtained forms the graphene film.
14. the preparation method of lithium ion battery negative material structure according to claim 13, it is characterised in that：By step 2) structure obtained, which is placed in reducing atmosphere, is heated to reaction temperature, and is passed through carbon-source gas into the reducing atmosphere with step The upper surface of the rapid structure 2) obtained forms the graphene film and specifically comprised the following steps：
3-1) structure for obtaining step 2) is placed in tube furnace；
Reducibility gas 3-2) is passed through into the tube furnace, the structure that step 2) is obtained is heated to the reaction temperature and protected Temperature, and carbon-source gas are passed through into the tube furnace in insulating process, formed with the upper surface of the structure obtained in step 2) The graphene film.
15. the preparation method of lithium ion battery negative material structure according to claim 14, it is characterised in that：Step 3- 1) and step 3-2) between also include the step of being cleaned to reducibility gas pipeline.
16. the preparation method of lithium ion battery negative material structure according to claim 14, it is characterised in that：Step 3- 2) in, the reducibility gas being passed through into the tube furnace includes hydrogen, the mixed gas of hydrogen and nitrogen or hydrogen and argon gas Mixed gas.
17. the preparation method of lithium ion battery negative material structure according to claim 14, it is characterised in that：Step 3- 2) in, the carbon-source gas being passed through into the tube furnace include at least one of methane, ethene, acetylene, ethanol or hexamethylene.
18. the preparation method of lithium ion battery negative material structure according to claim 14, it is characterised in that：Step 3- 2) in, the reaction temperature is 500 DEG C~1000 DEG C.
19. the preparation method of lithium ion battery negative material structure according to claim 14, it is characterised in that：Step 3- 2) in, soaking time is 5min~30min.
20. a kind of lithium ion battery negative material structure, it is characterised in that the lithium ion battery negative material structure includes：
Metal catalytic substrate；
Curing material layer, positioned at the upper surface of the metal catalytic substrate；The curing material layer is to include silicon nano material, carbon The composite layer of nano material and additive；
Graphene film, positioned at the upper surface of the curing material layer.
21. lithium ion battery negative material structure according to claim 20, it is characterised in that：The metal catalytic substrate Material for gold, platinum, palladium, iridium, ruthenium, nickel, one kind in copper or at least two alloy material or have the above coat of metal or Other metal foil substrate materials of alloy layer.
22. the lithium ion battery negative material structure according to right wants 20, it is characterised in that：The silicon nano material includes At least one of nano silicon particles, silicon nanowires or silicon nanofiber.
23. lithium ion battery negative material structure according to claim 20, it is characterised in that：The carbon nanomaterial bag Include at least one of CNT, carbon nano-fiber, graphene powder or fullerene.
24. lithium ion battery negative material structure according to claim 20, it is characterised in that：The additive includes leading At least one of electric additive, binding agent and stabilizer.
25. lithium ion battery negative material structure according to claim 24, it is characterised in that：The conductive additive bag Include at least one of acetylene black or graphite.
26. a kind of negative electrode of lithium ion battery, it is characterised in that the negative electrode of lithium ion battery is included as in claim 20 to 25 Lithium ion battery negative material structure described in any one.
27. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes lithium-ion electric as claimed in claim 26 Pond negative pole.
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