CN106602036A - Carbon core/copper oxide housing composite electrode for lithium ion battery and preparation method thereof - Google Patents
Carbon core/copper oxide housing composite electrode for lithium ion battery and preparation method thereof Download PDFInfo
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- CN106602036A CN106602036A CN201710037810.8A CN201710037810A CN106602036A CN 106602036 A CN106602036 A CN 106602036A CN 201710037810 A CN201710037810 A CN 201710037810A CN 106602036 A CN106602036 A CN 106602036A
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- copper oxide
- carbon fiber
- copper
- lithium ion
- carbon
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- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 239000005751 Copper oxide Substances 0.000 title claims abstract description 75
- 229910000431 copper oxide Inorganic materials 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000002131 composite material Substances 0.000 title abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims abstract description 72
- 239000004917 carbon fiber Substances 0.000 claims abstract description 72
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000465 moulding Methods 0.000 claims abstract description 17
- 238000005245 sintering Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052802 copper Inorganic materials 0.000 claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 11
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000004140 cleaning Methods 0.000 claims description 13
- 238000007654 immersion Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 230000001235 sensitizing effect Effects 0.000 claims description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- 230000008859 change Effects 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000007747 plating Methods 0.000 claims description 6
- 230000003213 activating effect Effects 0.000 claims description 5
- 229910052927 chalcanthite Inorganic materials 0.000 claims description 5
- 230000002706 hydrostatic effect Effects 0.000 claims description 5
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 claims description 5
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 230000004913 activation Effects 0.000 claims description 4
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 239000003292 glue Substances 0.000 claims description 4
- 238000007788 roughening Methods 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 206010070834 Sensitisation Diseases 0.000 claims description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 3
- 238000009990 desizing Methods 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 230000008313 sensitization Effects 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 239000002086 nanomaterial Substances 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 230000001351 cycling effect Effects 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910052744 lithium Inorganic materials 0.000 description 12
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 230000002441 reversible effect Effects 0.000 description 10
- 239000003792 electrolyte Substances 0.000 description 6
- 239000013543 active substance Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000012634 fragment Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 241000549556 Nanos Species 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002482 conductive additive Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009466 transformation Effects 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
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
-
- 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
- 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 invention discloses a carbon core/copper oxide housing composite electrode for a lithium ion battery and a preparation method thereof. A core part of the carbon core/copper oxide housing composite electrode is formed by carbon fibers, and a housing of the carbon core/copper oxide housing composite electrode is a copper oxide thin layer; and the copper oxide thin layer is provided with nano needle-shaped structures and nano pore-shaped structures, which are arranged in an array mode. The preparation method of the carbon core/copper oxide housing composite electrode comprises the following steps of: (1) preparation of copper-coated carbon fibers; (2) sintering moulding of the copper-coated carbon fibers; and (3) surface oxidation treatment of a formed copper-coated carbon fiber felt. According to the carbon core/copper oxide housing composite electrode disclosed by the invention, charging and discharging capacity of the lithium ion battery is improved, and electrochemical properties of a cycle life, coulombic efficiency, cycling stability and the like of the lithium ion battery are improved.
Description
Technical field
The present invention relates to technical field of lithium ion, and in particular to a kind of carbon core/copper oxide for lithium ion battery
Shell combination electrode and preparation method thereof.
Background technology
Lithium ion battery belongs to the chargeable electrochmical power source of green high-capacity, with voltage it is high, energy density is big, cycle performance
The outstanding advantages such as good, the little, memory-less effect of self discharge, in vehicle, portable electric appts, communication back-up source, sky
Between the field such as technology, national defense industry be widely applied.
Carbons material is the negative material being most widely used in current lithium ion battery, with suitable intercalation potential
（0.15 ~ 0.25V）, good conductivity, stable circulation, and also aboundresources, it is cheap, become the market mainstream for a long time.But
The theoretical specific capacity of carbons material is relatively low（372mAh·g-1）, can not meet too high demand of the people to the energy, therefore people
It is good in the urgent need to storing up lithium performance, the high novel active of theoretical capacity substitutes traditional graphite material and is applied to lithium-ion electric
Pond field, to solve the energy in straitened circumstances situation that supply falls short of demand.Transition metal oxide is as its storage lithium performance is good, theoretical capacity
The advantages of high, preparation is simply, raw material sources are extensive causes the strong interest of numerous researchers at home and abroad.Copper oxide conduct
Modal transition metal oxide, due to the higher (674mAhg of its theoretical specific capacity-1), to prepare simple, cost more low
Advantage, has gradually been applied in lithium ion battery.But the electric conductivity of copper oxide is poor, therefore live pure zirconia copper as negative pole
Property material can inevitably result in cycle life, coulombic efficiency and the stable charge/discharge of battery in being applied to lithium ion battery
Decline.In order to solve this problem, numerous researchers at present mainly by add conductive additive, synthetic composite material and
The methods such as modification activities physical form are improving copper oxide as the combination property of the battery of negative electrode active material.Such as by adding
Plus the conductive material such as electrically conductive graphite, CNT, metal dust is improving the electric conductivity of electrode, by synthesizing CuO composite Nanos
The structures such as line, nanometer rods, nano flower are improving cycle life and reversible capacity of battery etc..These methods are all to a certain degree
On solve the problems, such as CuO poorly conductives and cause battery performance to decline.
Additionally, lithium ion battery is during cycle charge-discharge, the embedding and removing process inside active substance can not be kept away
The expansion and contraction of active material particle volume can be caused with exempting from, so as to cause the powder phenomenon-tion of electrode material, affect battery
Cycle life.Therefore, change in volume of the restricted activity material during embedding and removing undoubtedly extends battery cycle life,
Improve the effective means of battery combination property.Than if any researcher by one layer of carbon thin layer of silicon grain surface carbonation limiting
The violent change in volume of silicon grain in battery charge and discharge process, so as to improve the cycle life and reversible capacity of battery.Also learn
Person makes silicon grain surface realize metallization by electroless copper method, so as to improve every chemical property of lithium ion battery.
The content of the invention
In order to CuO be improved as the electric conductivity of electrode during cell negative electrode material, limit carbons active substance in battery charge and discharge
The change of the volume in electric process, so as to improve the electrochemistries such as the reversible capacity of battery, cycle life, stable charge/discharge
Can, the invention provides a kind of carbon core/copper oxide shell combination electrode for lithium ion battery.
The present invention also provides a kind of preparation side of carbon core/copper oxide shell combination electrode for lithium ion battery
Method.
The present invention is achieved through the following technical solutions.
A kind of carbon core/copper oxide shell combination electrode for lithium ion battery, core is carbon fiber, and shell is copper oxide
Thin layer；Described copper oxide lamina has the nano whiskers structure and nanometer cavernous structure of array type；The nano whiskers structure
In the outer surface of copper oxide lamina, hole of the nanometer cavernous structure for insertion copper oxide lamina.
A kind of preparation method of described carbon core/copper oxide shell combination electrode for lithium ion battery, including copper facing
The surface oxidation treatment of the preparation of carbon fiber, the sinter molding of copper carbon fiber and molding copper carbon fiber felt.
Further, the preparation of the copper carbon fiber, comprises the steps：
（1）Desizing：Carbon fiber is placed in into calcination in high temperature resistance furnace air, the Protection glue of carbon fiber surface is removed, is carried
High coating and the adhesion of carbon fiber, reduce the contact resistance between coating and carbon fiber；
（2）Surface coarsening：Carbon fiber after calcination is placed in into (NH4)2S2O8In solution, ultrasound wave immersion, makes carbon fiber surface thick
Change and in hydrophilic；Subsequently soaked with NaOH solution, remove the remaining (NH of carbon fiber surface4)2S2O8, then deionized water is clear
Wash；
（3）Surface sensitizing：Carbon fiber after roughening is placed in by SnCl2, HCl and H2Soak in the sensitizing solution that O is formulated, so
Deionized water carries out hydrostatic rinsing afterwards；
（4）Surface active：Carbon fiber after sensitization is placed in by AgNO3、NH3·H2O and H2Soak in the activating solution that O is formulated
Bubble, then deionized water cleans carbon fiber to black；
（5）Copper coating：Carbon fiber after activation is placed in by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and
H2In the plating solution that O is formulated, produced with magnetic stirrer to solution bubble-free, last deionized water cleaning, vacuum
Drying, obtains the copper carbon fiber.
Further, step（1）In, the length of the carbon fiber is 1 ~ 2mm.
Further, step（1）In, the calcination is 30 ~ 40min of calcination at 400 ~ 500 DEG C.
Further, step（2）In, (the NH4)2S2O8The concentration of solution is 15 ~ 17wt%.
Further, step（2）In, in (NH4)2S2O8In solution, the time of ultrasound wave immersion is 30 ~ 40min.
Further, step（2）In, the concentration of the NaOH solution is 9 ~ 11wt%.
Further, step（2）In, the time soaked in NaOH solution is 5 ~ 10min.
Further, step（2）In, the deionized water cleaning is cleaned to cleaning mixture in neutrality.
Further, step（3）In, by SnCl2, HCl and H2In the sensitizing solution that O is formulated, SnCl2Concentration be
0.01~0.02g·mL-1, the concentration of HCl is 38 ~ 40mLL-1。
Further, step（3）In, the time of the immersion is 5 ~ 10min.
Further, step（3）In, the number of times of the hydrostatic rinsing is 3 ~ 4 times.
Further, step（4）In, by AgNO3、NH3·H2O and H2In the activating solution that O is formulated, AgNO3It is dense
Spend for 0.004 ~ 0.005gmL-1、NH3Concentration be 9 ~ 10mLL-1。
Further, step（4）In, the time of the immersion is 5 ~ 10min.
Further, step（5）In, by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and H2O prepare and
Into plating solution in, NaKC4H4O6Concentration be 0.04 ~ 0.05gmL-1, CuSO4Concentration be 0.01 ~ 0.02gmL-1, HCHO
Concentration be 9 ~ 10mLL-1, the concentration of NaOH is 0.01 ~ 0.02 gmL-1。
Further, step（5）In, the rotating speed of the magnetic stirrer is 300 ~ 400rmin-1。
Further, step（5）In, the deionized water cleaning is cleaned to cleaning mixture in neutrality.
Further, step（5）In, the vacuum drying is 5 ~ 6h of baking at 50 ~ 60 DEG C.
Further, the copper carbon fiber sinter molding, comprises the steps：
Copper carbon fiber is pressed into into fiber felt with mould, is placed in vacuum resistance furnace, high temperature sintering, obtain molding coppered carbon fine
Dimension felt.
Further, a diameter of 14 ~ 15mm of the carbon fiber felt, thickness are 0.1 ~ 0.2mm.
Further, the sintering is to carry out in a hydrogen atmosphere.
Further, the temperature of the sintering is 750 ~ 800 DEG C, and the time of sintering is 60 ~ 70min.
Further, the surface oxidation treatment of the molding copper carbon fiber felt, comprises the steps：
Molding copper carbon fiber felt is placed in Muffle furnace, air atmosphere high temperature heated oxide, obtains described for lithium ion
The carbon core of battery/copper oxide shell combination electrode.
Further, the temperature of the heated oxide is 400 ~ 450 DEG C, and the time is 1 ~ 2h.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）The present invention is used in the carbon core/copper oxide shell combination electrode of lithium ion battery, the poroid knot of nanometer of copper oxide lamina
Structure is conducive to the lithium ion in electrolyte to easily pass through, and then embedding and removing process occurs in carbon core, so as to increase lithium from
The charge/discharge capacity of sub- battery；
（2）Carbon core/copper oxide shell combination electrode of the present invention for lithium ion battery, carbon core segment are tight with copper oxide shell
Contact, had both improve the electric conductivity of electrode, had buffered the change in volume degree in copper oxide conversion process again；
（3）Carbon core/copper oxide shell combination electrode of the present invention for lithium ion battery, copper oxide shell are closely wrapped in carbon
Core segment, and the nano whiskers structure of copper oxide shell highly shortened the diffusion length of lithium ion and increased and lithium ion
Between effective contact area, limit the expansion of carbon fiber volume during lithium ion battery discharge and recharge embedding and removing, from
And be conducive to improving the reversible capacity and cycle life of lithium ion battery.
Description of the drawings
The overall structure diagram of carbon core/copper oxide shell combination electrodes of the Fig. 1 to prepare in embodiment 1；
The partial schematic diagram of carbon core/copper oxide shell combination electrodes of the Fig. 2 to prepare in embodiment 1；
Fig. 3 is the assembling schematic diagram of the lithium ion half-cell equipped with carbon core/copper oxide shell combination electrode in embodiment 2；
Fig. 4 is that the cycle charge discharge electrical testing of the lithium ion half-cell equipped with carbon core/copper oxide shell combination electrode in embodiment 2 is bent
Line chart.
Specific embodiment
To further understand the present invention, the present invention will be further described with reference to the accompanying drawings and examples, 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 carbon core/copper oxide shell combination electrode for lithium ion battery, comprises the steps：
The preparation of copper carbon fiber
（1）Desizing：Carbon fiber of the length for 1mm is placed in into calcination 30min in high temperature resistance furnace air, calcination temperature is
400 DEG C, to remove the Protection glue of carbon fiber surface, the adhesion of coating and carbon fiber is improved, reduced between coating and carbon fiber
Contact resistance；
（2）Surface coarsening：Carbon fiber after removing glue is placed in into (the NH that concentration is 15wt%4)2S2O8Ultrasound wave immersion in solution
30min, makes carbon fiber surface roughening and in hydrophilic；5min is soaked to which with the NaOH solution that concentration is 10wt% subsequently, is removed
Remaining (the NH of carbon fiber surface4)2S2O8, and carbon fiber is cleaned to cleaning mixture in neutrality；
（3）Surface sensitizing：Carbon fiber after roughening is placed in by SnCl2, HCl and H2The sensitizing solution that O is formulated（Sensitizing solution
In, SnCl2Concentration be 0.02gmL-1, the concentration of HCl is 40mLL-1）Middle immersion 10min, then deionized water is to carbon
Fiber carries out hydrostatic and rinses 3 times；
（4）Surface active：Carbon fiber after sensitization is placed in by AgNO3、NH3·H2O and H2The activating solution that O is formulated（Activation
In liquid, AgNO3Concentration be 0.005gmL-1, NH3·H2The concentration of O is 10mLL-1）Middle immersion 10min, then spend from
Sub- water cleans carbon fiber to black；
（5）Copper coating：Carbon fiber after activation is placed in by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and
H2The plating solution that O is formulated（In plating solution, NaKC4H4O6Concentration be 0.04gmL-1, CuSO4Concentration be 0.01gmL-1,
The concentration of HCHO is 10mLL-1, the concentration of NaOH is 0.01gmL-1）In, with magnetic stirring apparatuss with 400rmin-1Turn
Speed is stirred to solution bubble-free and is produced, and last deionized water cleans to cleaning mixture copper carbon fiber in neutrality, and vacuum 60
DEG C drying 6h, obtain copper carbon fiber.
The sinter molding of copper carbon fiber
（6）Compacting：The copper carbon fiber of 50mg is pressed into into a diameter of 15mm, fiber felt of the thickness for 0.1mm；
（7）Sintering：The fiber felt of compacting is placed in vacuum resistance furnace, in a hydrogen atmosphere, high temperature sintering, sintering temperature is
800 DEG C, temperature retention time is 60min, obtains molding copper carbon fiber felt.
The surface oxidation treatment of molding copper carbon fiber felt
（8）The molding copper carbon fiber felt of gained is placed in Muffle furnace, in atmosphere high-temperature heating oxidation, heating-up temperature is
400 DEG C, temperature retention time is 2h, obtains the carbon core/copper oxide shell combination electrode for lithium ion battery.
The overall structure diagram of the carbon core for the lithium ion battery/copper oxide shell combination electrode for preparing and local show
It is intended to respectively as depicted in figs. 1 and 2, including core and shell, core is carbon fiber 11, and shell is copper oxide lamina；Copper oxide
Thin layer has the nano whiskers structure 9 and nanometer cavernous structure 10 of array type, appearance of the nano whiskers structure 9 in copper oxide lamina
Face, hole of the nanometer cavernous structure 10 for insertion copper oxide lamina.
Embodiment 2
Carbon core prepared by embodiment 1/copper oxide shell combination electrode assembles assembling schematic diagram such as Fig. 3 institutes of lithium ion half-cell
Show, it is multiple including upper battery case 1, shell fragment 2, pad 3, lithium piece 4, barrier film 5, electrolyte 6, lower battery case 7 and carbon core/copper oxide shell
Composite electrode 8；
Carbon core/copper oxide shell combination electrode 8 is placed on lower battery case 7, and electrolyte 6 is full of being combined by carbon core/copper oxide shell
Active substance is filled with the whole cavity constituted by electrode 8, lower battery case 7 and barrier film 5, whole cavity, electrolyte 6 directly soaks
Active substance on profit carbon core/copper oxide shell combination electrode 8；Lithium piece 4 is close on barrier film 5, the upper surface of lithium piece 4 by down to
On be sequentially placed pad 3 and shell fragment 2, pad 3 and shell fragment 2 play a part of to adjust pressure, and shell fragment 2 is tight with upper battery case 1
Contact to reduce contact resistance, it is ensured that the good electric conductivity of inside battery.
After the completion of the assembling of lithium ion half-cell, during electric discharge, lithium piece 4 starts de- lithium, and lithium ion enters into electrolysis through barrier film 5
In liquid 6, subsequently with carbon core/copper oxide shell combination electrode 8 on active contacts and occur transformation, be embodied in lithium from
Son is directly converted with 9 by electrolyte, and process of intercalation occurs through nanostructured 10 and then with 11；At the same time, electricity
It is sub successively to enter into lower battery case 7 through pad 3, shell fragment 2 and upper battery case 1, due to outside lower battery case 7 and carbon core/copper oxide
Shell combination electrode 8 is in close contact, thus electronics enter in the active substance of carbon core/copper oxide shell combination electrode 8 with lithium from
Son carries out charging neutrality, completes the discharge process of lithium ion half-cell；And the charging process of lithium ion half-cell is just contrary.
Described lithium ion half-cell in charge and discharge process, as the nano whiskers structure of copper oxide shell greatly contracts
The short diffusion length of lithium ion and the effective contact area between lithium ion is increased, thus the reversible capacity of battery can be with
It is greatly improved.Additionally, the nanometer cavernous structure of copper oxide is conducive to the lithium ion in electrolyte to easily pass through, Jin Er
There is embedding and removing process in carbon core, so as to increase the charge/discharge capacity of battery.During the cycle charge-discharge of battery, carbon
Core segment is in close contact with copper oxide shell, had both been improve the electric conductivity of electrode, and had been buffered the body in copper oxide conversion process again
Product intensity of variation；Copper oxide shell is closely wrapped in carbon core segment, during limiting embedding and removing to a certain extent
The change in volume of carbon core, so as to be conducive to improving the reversible capacity and cycle life of battery.
Charge-discharge test is circulated to the lithium ion half-cell for assembling with LAND battery test systems CT2001A, is obtained
Test curve it is as shown in Figure 4.As can be seen that there is carbon core/copper oxide shell combination electrode from curve（CuO-CF）Lithium from
Sub- battery is than only oxidation copper electrode（CuO）Only carbon fiber electrode（CF）Lithium ion battery have higher reversible capacity
With more preferable high rate performance.Wherein there is the current condition in 0.1C of the lithium ion battery of carbon core/copper oxide shell combination electrode
Under reversible specific capacity be up to 671.2mAh/g, significantly larger than only oxidation copper electrode and the only lithium-ion electric of carbon fiber electrode
Pond.Under the conditions of different multiplying powers, there is the reversible capacity of lithium ion battery of carbon core/copper oxide shell combination electrode relative to which
His two kinds of batteries also very advantageous.Additionally, after 0.1C, 0.2C, 0.5C, 1C and 2C rate charge-discharge, having carbon core/copper oxide
The lithium ion battery of shell combination electrode reversible capacity under the current condition of 0.1C is still maintained at 637.4 mAh/g, accounts for again
The 94.8% of the stable capacity of battery before rate discharge and recharge, as a result show carbon core/copper oxide shell combination electrode can effectively improve lithium from
Every chemical property of sub- 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 (10)
1. a kind of carbon core/copper oxide shell combination electrode for lithium ion battery, it is characterised in that the carbon core/copper oxide
The core of shell combination electrode is carbon fiber, and shell is copper oxide lamina；Described copper oxide lamina has the needle-like of array type
Structure and cavernous structure；Described acicular texture and cavernous structure are nano-scale structures；The acicular texture is in copper oxide
The outer surface of thin layer, hole of the cavernous structure for insertion copper oxide lamina.
2. the preparation method of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery described in claim 1, its
It is characterised by, the Surface Oxygen of the sinter molding and molding copper carbon fiber felt of preparation, copper carbon fiber including copper carbon fiber
Change is processed.
3. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 2
Method, it is characterised in that the preparation of the copper carbon fiber, comprises the steps：
（1）Desizing：Carbon fiber is placed in into calcination in high temperature resistance furnace air, the Protection glue of carbon fiber surface is removed；
（2）Surface coarsening：Carbon fiber after calcination is placed in into (NH4)2S2O8In solution, ultrasound wave immersion, subsequently uses NaOH solution
Immersion, removes the remaining (NH of carbon fiber surface4)2S2O8, then deionized water cleaning；
（3）Surface sensitizing：Carbon fiber after roughening is placed in by SnCl2, HCl and H2Soak in the sensitizing solution that O is formulated, so
Deionized water carries out hydrostatic rinsing afterwards；
（4）Surface active：Carbon fiber after sensitization is placed in by AgNO3、NH3·H2O and H2Soak in the activating solution that O is formulated
Bubble, then deionized water cleans carbon fiber to black；
（5）Copper coating：Carbon fiber after activation is placed in by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and H2O
In the plating solution being formulated, produced with magnetic stirrer to solution bubble-free, last deionized water cleaning, vacuum are dried
It is dry, obtain the copper carbon fiber.
4. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 3
Method, it is characterised in that step（1）In, the length of the carbon fiber is 1 ~ 2mm, and the calcination is the calcination 30 at 400 ~ 500 DEG C
~40min；Step（2）In, (the NH4)2S2O8The concentration of solution is 15 ~ 17wt%, in (NH4)2S2O8Ultrasound wave immersion in solution
Time be 30 ~ 40min, the concentration of the NaOH solution is 9 ~ 11wt%, and the time soaked in NaOH solution is 5 ~ 10min,
The deionized water cleaning is cleaned to cleaning mixture in neutrality.
5. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 3
Method, it is characterised in that step（3）In, by SnCl2, HCl and H2In the sensitizing solution that O is formulated, SnCl2Concentration be 0.01 ~
0.02g·mL-1, the concentration of HCl is 38 ~ 40mLL-1；The time of the immersion is 5 ~ 10min, the number of times of the hydrostatic rinsing
For 3 ~ 4 times；Step（4）In, by AgNO3、NH3·H2O and H2In the activating solution that O is formulated, AgNO3Concentration be 0.004 ~
0.005g·mL-1、NH3Concentration be 9 ~ 10mLL-1；The time of the immersion is 5 ~ 10min.
6. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 3
Method, it is characterised in that step（5）In, by NaKC4H4O6·4H2O、CuSO4·5H2O, HCHO, NaOH and H2What O was formulated
In plating solution, NaKC4H4O6Concentration be 0.04 ~ 0.05gmL-1, CuSO4Concentration be 0.01 ~ 0.02gmL-1, HCHO's is dense
Spend for 9 ~ 10mLL-1, the concentration of NaOH is 0.01 ~ 0.02 gmL-1；The rotating speed of the magnetic stirrer be 300 ~
400r·min-1；The deionized water cleaning is cleaned to cleaning mixture in neutrality；It is described vacuum drying be at 50 ~ 60 DEG C dry 5 ~
6h。
7. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 2
Method, it is characterised in that the copper carbon fiber sinter molding, comprises the steps：
Copper carbon fiber is pressed into into fiber felt with mould, is placed in vacuum resistance furnace, high temperature sintering, obtain molding coppered carbon fine
Dimension felt.
8. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 7
Method, it is characterised in that a diameter of 14 ~ 15mm of the copper carbon fiber felt, thickness are 0.1 ~ 0.2mm；The sintering is in hydrogen
Carry out under gas atmosphere；The temperature of the sintering is 750 ~ 800 DEG C, and the time of sintering is 60 ~ 70min.
9. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 2
Method, it is characterised in that the surface oxidation treatment of the molding copper carbon fiber felt, comprises the steps：
Molding copper carbon fiber felt is placed in Muffle furnace, air atmosphere high temperature heated oxide, obtains described for lithium ion
The carbon core of battery/copper oxide shell combination electrode.
10. the preparation side of a kind of carbon core/copper oxide shell combination electrode for lithium ion battery according to claim 9
Method, it is characterised in that the temperature of the heated oxide is 400 ~ 450 DEG C, the time is 1 ~ 2h.
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