CN106601996A - Multilayer nano-composite electrode for lithium ion battery and preparation method thereof - Google Patents
Multilayer nano-composite electrode for lithium ion battery and preparation method thereof Download PDFInfo
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- CN106601996A CN106601996A CN201710036957.5A CN201710036957A CN106601996A CN 106601996 A CN106601996 A CN 106601996A CN 201710036957 A CN201710036957 A CN 201710036957A CN 106601996 A CN106601996 A CN 106601996A
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000002114 nanocomposite Substances 0.000 title abstract 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000013543 active substance Substances 0.000 claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 29
- 239000010703 silicon Substances 0.000 claims abstract description 29
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052802 copper Inorganic materials 0.000 claims abstract description 25
- 239000010949 copper Substances 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000151 deposition Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 6
- 238000005253 cladding Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 9
- 230000008021 deposition Effects 0.000 claims description 8
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 7
- 229960004643 cupric oxide Drugs 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000009413 insulation Methods 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229940068984 polyvinyl alcohol Drugs 0.000 claims description 5
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 5
- 229910000077 silane Inorganic materials 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005229 chemical vapour deposition Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 5
- 239000005751 Copper oxide Substances 0.000 abstract description 4
- 229910000431 copper oxide Inorganic materials 0.000 abstract description 4
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 239000002482 conductive additive Substances 0.000 abstract description 2
- 230000006872 improvement Effects 0.000 abstract description 2
- 230000002441 reversible effect Effects 0.000 abstract description 2
- 239000000853 adhesive Substances 0.000 abstract 1
- 230000001070 adhesive effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000012634 fragment Substances 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical group [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- WCCJDBZJUYKDBF-UHFFFAOYSA-N copper silicon Chemical compound [Si].[Cu] WCCJDBZJUYKDBF-UHFFFAOYSA-N 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- 230000010339 dilation Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002052 molecular layer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/366—Composites as layered products
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
-
- 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
- H01M2004/021—Physical characteristics, e.g. porosity, surface area
-
- 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
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- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
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- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
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- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a multilayer nano-composite electrode for a lithium ion battery and preparation method thereof. The multilayer nano-composite electrode is mainly composed of a copper current collector and multilayer active substances; the copper current collector is provided with a porous structure and a nano-needle structure; the multilayer active substances comprise a silicon layer and a carbon layer. The preparation method of the multilayer nano-composite electrode is as follows: (1) sintering of copper powder; (2) growing and reducing of copper oxide nanoneedle structure; (3) depositing of a silicon nanometer layer; and (4) cladding of the carbon nanometer layer. The multilayer nano-composite electrode disclosed by the invention can effectively limit the sharp change of the volume of silicon active substance in the charging/discharging process of the battery, thereby prolonging the cycle life of the battery; and meanwhile, the porous structure and the nano-needle structure of the current collector are directly and tightly contacted with the active substances, the use of each of the adhesive and the conductive additive is reduced, thereby facilitating the improvement of the reversible capacity, the coulombic efficiency, the cycle stability and other electrochemical properties of the battery.
Description
Technical field
The present invention relates to technical field of lithium ion, specifically a kind of multi-layer nano compound electric for lithium ion battery
Pole and preparation method thereof.
Background technology
Lithium ion battery comes out only less than 30 years, compared to the chargeable nickel-cadmium cell of valve-regulated lead-acid battery or ni-mh
For battery, lithium ion battery is excellent with the high heavy-current discharge applicable in extensive range and excellent of its unit energy density etc.
Gesture becomes the outstanding person in these secondary cells.The beginning of the new century, with development and the development of new forms of energy power vehicle, reduces the energy
Consumption bring environmental pollution, substitute based on Fossil fuel outmoded energy resource structure be the purpose energy reform advance, with
Lithium ion battery is just obtaining extensive approval and is receiving for the energy framework of core.
The negative pole of lithium ion battery should have following features：Electrode potential is relatively low, can keep a stable platform, makes
Lithium ion battery can obtain stable output voltage；Theoretical specific capacity is high as much as possible, exactly can have more lithiums from
Son is embedded and deviates from；In slotting lithium and de- lithium, its structure should keep constant or vary less material, so as to ensure that battery has
Good cycle performance；With good electron conduction and fast lithium ion transport speed, battery polarization can be so reduced,
Under big multiplying power electric current density during discharge and recharge, battery still can have high specific capacity；Interface performance is excellent, can be with electrolysis
Liquid forms stable and good solid electrolyte interface film (SEI films)；Easily preparation, abundance, low cost, nontoxic, safe
And environmental friendliness.The lithium ion battery negative pole active materials for being used at present are graphite, but the theoretical specific capacity of graphite is not high,
Growing energy requirement cannot be met.Silicon is more than as active substance with very high theoretical specific capacity, but volumetric expansion
300%, cause active substance powder of detached, irreversible capacity to increase, battery life is short.Many researchers are by carbon silicon core-shell nano
Structure can be very good the expansion for limiting silicon volume as active substance, but the resistance of active substance is larger, and battery performance is low.
Also researcher works out the electrode containing copper silicon nanometer nuclear shell nano-structure, but the dilation of silicon causes the de- of silicon nano material
Fall.All contain conductive agent, binding agent etc. in traditional active substance coating to the inoperative material of battery capacity, not only reduce
Battery effectively utilizes volume, also add the resistance of active substance.
The content of the invention
In order to improve the capacity of lithium ion battery, the volumetric expansion of silicon is effectively limited, improve the electric conductivity of electrode, subtracted
The use of few binding agent and conductive additive, so as to be conducive to improving reversible capacity, coulombic efficiency, cyclical stability of battery etc.
Chemical property, the invention provides a kind of multi-layer nano combination electrode for lithium ion battery.
Present invention also offers a kind of preparation method of multi-layer nano combination electrode for lithium ion battery.
The present invention is achieved through the following technical solutions.
A kind of multi-layer nano combination electrode for lithium ion battery, mainly by copper current collector and multilamellar active matter quality structure
Into；The copper current collector is made up of copper powder particle；
The copper current collector has loose structure and nano whiskers structure；The loose structure is present between copper powder particle；Institute
Nano whiskers structure is stated on the surface of copper powder particle；
The multilamellar active substance is coated on the outer surface of the copper powder particle with nano whiskers structure；The multilamellar active substance bag
Silicon nanometer layer and carbon nanometer layer are included, the carbon nanometer layer is coated on the outer surface of silicon nanometer layer.
A kind of preparation method of described multi-layer nano combination electrode for lithium ion battery, comprises the steps：
（1）The sintering of copper powder：Weigh copper powder to be placed in graphite jig, in being put into vacuum resistance furnace, high temperature sintering obtains sintering sample
Product；
（2）The growth of cupric oxide nano acicular texture and reduction：Sintered sample is placed in Muffle furnace, after high-temperature heating, then is put
In vacuum resistance furnace, thermal reduction is added under hydrogen atmosphere, obtain the copper current collector；
（3）The deposition of silicon nanometer layer：Copper current collector is placed in into chemical vapor deposition reactor（CVD）It is interior, it is passed through pure silane
（SiH4）, complete the deposition of silicon nanometer layer；
（4）The cladding of carbon nanometer layer：The copper current collector that deposited silicon nanometer layer is placed in poly-vinyl alcohol solution and is soaked, vacuum is done
After dry, it is placed in vacuum resistance furnace, heating and thermal insulation under protective atmosphere, obtains the multi-layer nano for lithium ion battery and be combined
Electrode.
Further, step（1）In, the temperature of the high temperature sintering is 800 ~ 900 DEG C, and the time is 1 ~ 2h.
Further, step（1）In, the high temperature sintering is to carry out in a hydrogen atmosphere.
Further, step（2）In, the temperature of the high-temperature heating is 400 ~ 700 DEG C, and the time is 5 ~ 7h.
Further, step（2）In, the high-temperature heating is to carry out in air atmosphere.
Further, step（2）In, the temperature of described plus thermal reduction is 250 ~ 300 DEG C, and the time is 2 ~ 2.5h.
Further, step（3）In, the intake of the pure silane is 4 ~ 7ml/min.
Further, step（3）In, the deposition process parameter in the chemical vapor deposition reactor is：Pressure 75 ~
80Pa, 200 DEG C ~ 250 DEG C of temperature, 30 ~ 40min of time, 74 ~ 76mW/cm of radio-frequency power2。
Further, step（4）In, the mass concentration of the poly-vinyl alcohol solution is 4wt% ~ 5wt%.
Further, step（4）In, the time of the immersion is 2 ~ 3h.
Further, step（4）In, the vacuum drying is that 6 ~ 7h is dried at 60 ~ 70 DEG C.
Further, step（4）In, the protective atmosphere is argon gas atmosphere.
Further, step（4）In, the temperature of the heating and thermal insulation is 200 ~ 250 DEG C, and the time of insulation is 2 ~ 3h.
Compared with prior art, it is of the invention to have the advantage that：
（1）In multi-layer nano combination electrode of the present invention, the copper nanoneedle on copper current collector is combined with active substance, is effectively increased
The conductive capability of active substance, so as to improving the charge-discharge performance of battery；
（2）In multi-layer nano combination electrode of the present invention, silicon nanolayer deposition has dispersion to make in copper nanoneedle to silicon nanostructure
With while also serving as the support skeleton of silicon nano material, the intensity of silicon nano material being enhanced, so as to increase lithium ion battery
Life-span；
（3）In multi-layer nano combination electrode of the present invention, carbon nanomaterial is coated on silicon nano material, effectively limit silicon material
The volumetric expansion of material, reduces coming off for silicon active substance, reduces the irreversible capacity of lithium ion battery, increases lithium ion battery
Life-span；
（4）There is no the compositions such as binding agent, conductive agent using active substance in the multi-layer nano combination electrode of the present invention, increase lithium
The energy density of ion battery, reduces the resistance of active substance, improves the performance of lithium ion battery；
（5）Active substance is adopted for monodimension nanometer material, shorten lithium ion and enter work in multi-layer nano combination electrode of the present invention
The distance of property material, increased lithium ion battery charge-discharge velocity.
Description of the drawings
Fig. 1 is the structural representation of multi-layer nano combination electrode prepared by embodiment 1；
Fig. 2 is the microstructure schematic diagram of the monomer particle of multi-layer nano combination electrode prepared by embodiment 1；
Fig. 3 is the assembling schematic diagram of lithium ion half-cell of the embodiment 2 equipped with multi-layer nano combination electrode.
Specific embodiment
To further understand the present invention, with reference to the accompanying drawings and examples the present invention will be further described, however it is necessary that
Illustrate, the scope of protection of present invention is not limited to the scope of embodiment statement, right intrinsic parameter
Other unrequited embodiments are equally effective.
Embodiment 1
A kind of preparation of the novel multi-layer nanometer combined electrode for lithium ion battery, comprises the steps：
（1）The sintering of copper powder：Weigh copper powder to be placed in the graphite jig of customization, in being then placed into vacuum resistance furnace, in hydrogen
High temperature sintering under environment, sintering temperature is 900 DEG C, and temperature retention time is 2h；
（2）The growth of cupric oxide nano pin：Sample after sinter molding is placed in Muffle furnace, in atmosphere high-temperature heating, plus
Hot temperature is 500 DEG C, and temperature retention time is 7h, obtains growing the copper oxide for having nanoneedle；
（3）The reduction of cupric oxide nano pin：The copper oxide that growth has nanoneedle is placed in vacuum resistance furnace, under hydrogen environment
Reductive copper oxide nanoneedle, heating-up temperature is 250 DEG C, and temperature retention time is 2h, obtains copper current collector；
（4）The deposition of silicon nanometer layer：Copper current collector is put in CVD reactors, the pure silane for being passed through 5ml per minute（SiH4）,
Reaction pressure is 75Pa, and temperature is 200 DEG C, and the time is 30min, and radio-frequency power is 75mW/cm2, complete the deposition of silicon nanometer layer；
（5）The cladding of carbon nanometer layer：The sample of gained is placed in the poly-vinyl alcohol solution that mass fraction is 5% and soaks 3h, then
In vacuum drying 7h, baking temperature is 60 DEG C；Dried sample is put in vacuum resistance furnace, the heating under ar gas environment is protected
Temperature, heating-up temperature is 250 DEG C, and temperature retention time is 3h.
The structural representation of the multi-layer nano combination electrode for preparing and the microstructure schematic diagram difference of monomer particle
As depicted in figs. 1 and 2, the multi-layer nano combination electrode is mainly made up of copper current collector and multilamellar active substance；Including copper nanometer
Acicular texture 9, copper powder particle 10, silicon nanometer layer 11 and carbon nanometer layer 12；
The copper current collector is made up of copper powder particle 10；The copper current collector has loose structure and nano whiskers structure 9；It is described
Loose structure is present between copper powder particle 10；The nano whiskers structure 9 is on the surface of copper powder particle 10；The multilamellar is lived
Property material is coated on the outer surface of the copper powder particle 10 with nano whiskers structure；The multilamellar active substance includes silicon nanometer layer 11
With carbon nanometer layer 12, the carbon nanometer layer 12 is coated on the outer surface of silicon nanometer layer 11.
Embodiment 2
Multi-layer nano combination electrode prepared by embodiment 1 be used for assemble lithium ion half-cell, assembling schematic diagram as shown in figure 3,
Including upper battery case 1, shell fragment 2, pad 3, lithium piece 4, barrier film 5, electrolyte 6, lower battery case 7 and novel multi-layer nanometer combined electrode
8；
Multi-layer nano combination electrode 8 is placed on lower battery case 7, the needle-like on the direct invasion multi-layer nano combination electrode 8 of electrolyte 6
The active substance of nanometer composite layer, electrolyte 6 is full of what is be made up of multi-layer nano combination electrode 8, lower battery case 7 and barrier film 5
Whole cavity；Lithium piece 4 is close on barrier film 5, and the upper surface of lithium piece 4 is sequentially placed from the bottom to top pad 3 and shell fragment 2, pad 3
Play a part of to adjust pressure with shell fragment 2；Shell fragment 2 is in close contact to reduce contact resistance with upper battery case 1, it is ensured that inside battery
Good electric conductivity.
After the completion of the assembling of lithium ion half-cell, during lithium ion half-cell discharge, lithium piece 4 starts de- lithium, lithium ion pass through every
Film 5 is entered in electrolyte 6, subsequently with multi-layer nano combination electrode 8 above acicular nanometer composite bed active contacts,
The embedding lithium reaction of generation；At the same time, electronics successively enters into lower battery case 7 through pad 3, shell fragment 2 and upper battery case 1, due to
Lower battery case 7 is in close contact with novel multi-layer nanometer combined electrode 8, thus electronics subsequently just to enter into novel multi-layer nano combined
Charging neutrality is carried out with lithium ion in the active substance of the acicular nanometer composite bed of electrode 8, the electric discharge of lithium ion half-cell is completed
Process.
When lithium ion half-cell charges, acicular nanometer of the lithium ion first from novel multi-layer nanometer combined electrode 8 is combined
The active substance the inside deintercalation of layer, in entering into electrolyte 6, is subsequently contacted by barrier film 5 with lithium piece 4；Electronics is from novel multi-layer
Active substance above nanometer combined electrode 8 is transferred out, successively through lower battery case 7, upper battery case 1, shell fragment 2 and pad 3
Charge balance is carried out with the lithium ion in lithium piece 4, charging process is completed.
Described lithium ion half-cell in charge and discharge process, because copper current collector has copper nanoneedle, with nano material
Active substance combine, enhance the electric conductivity of active substance；Active substance on multi-layer nano combination electrode is compound for silicon-carbon
Nanometer layer, greatly reduces battery Lithium-ion embeding and the activity caused when departing from active substance in charge and discharge process
Material powder phenomenon-tion, also shortens the distance that lithium ion enters active substance, increases lithium ion battery life-span and charge-discharge velocity；
Simultaneously the active substance of described novel multi-layer nanometer combined electrode does not contain the materials such as binding agent, reduces the electricity of active substance
Resistance, improves the energy density of lithium ion battery.
The above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not to the present invention
Embodiment restriction.For those of ordinary skill in the field, can also make on the basis of the above description
The change or variation of other multi-forms.There is no need to be exhaustive to all of embodiment.It is all the present invention
Any modification, equivalent and improvement made within spirit and principle etc., should be included in the protection of the claims in the present invention
Within the scope of.
Claims (8)
1. a kind of multi-layer nano combination electrode for lithium ion battery, it is characterised in that main to be lived by copper current collector and multilamellar
Property material constitute；The copper current collector is made up of copper powder particle；
The copper current collector has loose structure and nano whiskers structure；The loose structure is formed by between copper powder particle；Institute
Nano whiskers structure is stated on the surface of copper powder particle；
The multilamellar active substance is coated on the outer surface of the copper powder particle with nano whiskers structure；The multilamellar active substance bag
Silicon nanometer layer and carbon nanometer layer are included, the carbon nanometer layer is coated on the outer surface of silicon nanometer layer.
2. a kind of preparation method of the multi-layer nano combination electrode for lithium ion battery described in claim 1, its feature exists
In comprising the steps：
（1）The sintering of copper powder：Weigh copper powder to be placed in graphite jig, in being put into vacuum resistance furnace, high temperature sintering obtains sintering sample
Product；
（2）The growth of cupric oxide nano acicular texture and reduction：Sintered sample is placed in Muffle furnace, after high-temperature heating, then is put
In vacuum resistance furnace, thermal reduction is added under hydrogen atmosphere, obtain the copper current collector；
（3）The deposition of silicon nanometer layer：Copper current collector is placed in chemical vapor deposition reactor, pure silane is passed through, silicon is completed and is received
The deposition of rice layer；
（4）The cladding of carbon nanometer layer：The copper current collector that deposited silicon nanometer layer is placed in poly-vinyl alcohol solution and is soaked, vacuum is done
After dry, it is placed in vacuum resistance furnace, heating and thermal insulation under protective atmosphere, obtains the multi-layer nano for lithium ion battery and be combined
Electrode.
3. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（1）In, the temperature of the high temperature sintering is 800 ~ 900 DEG C, and the time is 1 ~ 2h；The high temperature sintering is in hydrogen
Carry out under gas atmosphere.
4. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（2）In, the temperature of the high-temperature heating is 400 ~ 700 DEG C, and the time is 5 ~ 7h；The high-temperature heating is in sky
Carry out under gas atmosphere.
5. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（2）In, the temperature of described plus thermal reduction is 250 ~ 300 DEG C, and the time is 2 ~ 2.5h.
6. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（3）In, the intake of the pure silane is 4 ~ 7ml/min；Deposition in the chemical vapor deposition reactor
Procedure parameter is：75 ~ 80Pa of pressure, 200 DEG C ~ 250 DEG C of temperature, 30 ~ 40min of time, 74 ~ 76mW/cm of radio-frequency power2。
7. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（4）In, the mass concentration of the poly-vinyl alcohol solution is 4wt% ~ 5wt%；The time of the immersion is 2 ~ 3h；
The vacuum drying is that 6 ~ 7h is dried at 60 ~ 70 DEG C.
8. the preparation method of a kind of multi-layer nano combination electrode for lithium ion battery according to claim 2, it is special
Levy and be, step（4）In, the protective atmosphere is argon gas atmosphere；The temperature of the heating and thermal insulation is 200 ~ 250 DEG C, insulation
Time is 2 ~ 3h.
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