CN106602036B - Carbon core/copper oxide shell composite electrode for lithium ion battery and preparation method thereof - Google Patents

Carbon core/copper oxide shell composite electrode for lithium ion battery and preparation method thereof Download PDF

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CN106602036B
CN106602036B CN201710037810.8A CN201710037810A CN106602036B CN 106602036 B CN106602036 B CN 106602036B CN 201710037810 A CN201710037810 A CN 201710037810A CN 106602036 B CN106602036 B CN 106602036B
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carbon fiber
copper
copper oxide
composite electrode
concentration
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CN106602036A (en
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袁伟
罗健
潘保有
邱志强
黄诗敏
闫志国
谭振豪
汤勇
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South China University of Technology SCUT
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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
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
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Abstract

The invention discloses a carbon core/copper oxide shell composite electrode for a lithium ion battery and a preparation method thereof. The core part of the carbon core/copper oxide shell composite electrode is carbon fiber, and the shell is a copper oxide thin layer; the copper oxide thin layer has an array type nanometer needle-shaped structure and a nanometer hole-shaped structure. The preparation method of the carbon core/copper oxide shell composite electrode comprises the following steps: (1) preparing copper-plated carbon fibers; (2) sintering and forming copper-plated carbon fibers; and (3) surface oxidation treatment of the formed copper-plated carbon fiber felt. The carbon core/copper oxide shell composite electrode improves the charge and discharge capacity of the lithium ion battery, and improves the electrochemical properties of the lithium ion battery, such as cycle life, coulomb efficiency, cycle stability and the like.

Description

Carbon core/copper oxide shell composite electrode for lithium ion battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a carbon core/copper oxide shell composite electrode for a lithium ion battery and a preparation method thereof.
Background
The lithium ion battery belongs to a green high-energy chargeable chemical power supply, has the outstanding advantages of high voltage, high energy density, good cycle performance, small self-discharge, no memory effect and the like, and is widely applied to the fields of vehicles, portable electronic equipment, backup power supplies for communication, space technology, national defense industry and the like.
The carbon material is the anode material which is most widely applied in the current lithium ion battery, has proper lithium intercalation potential (0.15-0.25V), has good conductivity, stable circulation, abundant resources and low price, and has long become the main stream of the market. However, the theoretical specific capacity of the carbon material is low (372 mAh.g -1 ) The method has the advantages that the method can not meet the excessively high energy demand of people, so that the novel active material with good lithium storage performance and high theoretical capacity is urgently needed to replace the traditional graphite material to be applied to the field of lithium ion batteries, and the embarrassing situation of energy supply and demand is solved. The transition metal oxide has strong interest of vast researchers at sea and abroad due to the advantages of good lithium storage performance, high theoretical capacity, simple preparation, wide sources of raw materials and the like. Copper oxide is the most common transition metal oxide due to its high theoretical specific capacity (674 mAh.g -1 ) The advantages of simple preparation, low cost and the like are achieved, and the method is gradually applied to lithium ion batteries. However, copper oxide has poor conductivity, and thus the application of pure copper oxide as a negative electrode active material in a lithium ion battery inevitably causes degradation of cycle life, coulombic efficiency, and charge-discharge stability of the battery. To solve this problem, a large number of researchers have now mainly used the addition of conductive additives, the synthesis of composite materials and the modification of active species morphologyAnd the like to improve the overall performance of the battery with copper oxide as the negative electrode active material. For example, the conductivity of the electrode is improved by adding conductive materials such as conductive graphite, carbon nanotubes, metal powder and the like, and the cycle life, reversible capacity and the like of the battery are improved by synthesizing structures such as CuO composite nanowires, nanorods, nanoflower and the like. These methods solve the problem of the decrease in battery performance due to poor CuO conductivity to some extent.
In addition, in the cyclic charge and discharge process of the lithium ion battery, the lithium intercalation and deintercalation process inside the active material inevitably causes the expansion and contraction of the volume of the active material particles, thereby causing the pulverization phenomenon of the electrode material and affecting the cycle life of the battery. Therefore, limiting the volume change of the active material during the lithium intercalation and deintercalation process is certainly an effective means for prolonging the cycle life of the battery and improving the comprehensive performance of the battery. There are researchers that limit the dramatic volume change of silicon particles during the charge and discharge of a battery by carbonizing a thin layer of carbon on the surface of the silicon particles, thereby improving the cycle life and reversible capacity of the battery. Also, scholars have achieved metallization of the silicon particle surfaces by electroless copper plating to improve various electrochemical properties of lithium ion batteries.
Disclosure of Invention
In order to improve the conductivity of an electrode when CuO is used as a battery cathode material and limit the volume change of a carbon active substance in the battery charging and discharging process, so as to improve the reversible capacity, the cycle life, the charging and discharging stability and other electrochemical performances of the battery, the invention provides a carbon core/copper oxide shell composite electrode for a lithium ion battery.
The invention also provides a preparation method of the carbon core/copper oxide shell composite electrode for the lithium ion battery.
The invention is realized by the following technical scheme.
The carbon core/copper oxide shell composite electrode for the lithium ion battery comprises a carbon fiber core and a copper oxide thin layer shell; the copper oxide thin layer has an array type nanometer needle-shaped structure and a nanometer hole-shaped structure; the nanometer needle-shaped structure is arranged on the outer surface of the copper oxide thin layer, and the nanometer hole-shaped structure is a hole penetrating through the copper oxide thin layer.
The preparation method of the carbon core/copper oxide shell composite electrode for the lithium ion battery comprises the steps of preparing copper-plated carbon fibers, sintering and forming the copper-plated carbon fibers and carrying out surface oxidation treatment on the formed copper-plated carbon fiber felt.
Further, the preparation of the copper-plated carbon fiber comprises the following steps:
(1) Surface photoresist removal: the carbon fiber is placed in the air in the high-temperature resistance furnace to be burnt, the protective glue on the surface of the carbon fiber is removed, the binding force between the plating layer and the carbon fiber is improved, and the contact resistance between the plating layer and the carbon fiber is reduced;
(2) Surface roughening: placing the burnt carbon fiber in (NH) 4 ) 2 S 2 O 8 Soaking in the solution by ultrasonic waves to coarsen and hydrophilize the surface of the carbon fiber; then soaking with NaOH solution to remove residual (NH) 4 ) 2 S 2 O 8 Cleaning with deionized water;
(3) Surface sensitization: placing the roughened carbon fiber in a catalyst consisting of SnCl 2 HCl and H 2 Soaking in sensitization solution prepared by O, and then rinsing with deionized water;
(4) Surface activation: placing the sensitized carbon fiber in a reactor consisting of AgNO 3 、NH 3 ·H 2 O and H 2 Soaking in an activating solution prepared by O, and then cleaning the carbon fiber to black by deionized water;
(5) Surface copper plating: placing activated carbon fiber in NaKC 4 H 4 O 6 ·4H 2 O、CuSO 4 ·5H 2 O, HCHO, naOH and H 2 And (3) in the plating solution prepared by the O, stirring the solution by using a magnetic stirrer until no bubbles are generated in the solution, and finally cleaning the solution by using deionized water and drying the solution in vacuum to obtain the copper-plated carbon fiber.
Further, in the step (1), the length of the carbon fiber is 1-2 mm.
Further, in the step (1), the firing is performed at 400-500 ℃ for 30-40 min.
Further, in the step (2), the (NH) 4 ) 2 S 2 O 8 The concentration of the solution is 15-17 wt%.
Further, in the step (2), in (NH) 4 ) 2 S 2 O 8 The ultrasonic soaking time in the solution is 30-40 min.
Further, in the step (2), the concentration of the NaOH solution is 9-11wt%.
Further, in the step (2), the time of soaking in the NaOH solution is 5-10 min.
Further, in the step (2), the deionized water is washed until the washing liquid is neutral.
Further, in the step (3), the catalyst is prepared from SnCl 2 HCl and H 2 In the sensitized liquid prepared by O, snCl 2 The concentration of (C) is 0.01-0.02 g.mL -1 HCl concentration of 38-40 mL.L -1 。
Further, in the step (3), the soaking time is 5-10 min.
Further, in the step (3), the number of times of the still water rinsing is 3 to 4.
Further, in the step (4), the method comprises the step of reacting AgNO 3 、NH 3 ·H 2 O and H 2 In the activating solution prepared by O, agNO 3 The concentration of (C) is 0.004-0.005 g/mL -1 、NH 3 The concentration of (C) is 9-10 mL.L -1 。
Further, in the step (4), the soaking time is 5-10 min.
Further, in the step (5), the catalyst is prepared from NaKC 4 H 4 O 6 ·4H 2 O、CuSO 4 ·5H 2 O, HCHO, naOH and H 2 In the plating solution prepared by O, naKC 4 H 4 O 6 The concentration of (C) is 0.04-0.05 g.mL -1 ，CuSO 4 The concentration of (C) is 0.01-0.02 g.mL -1 HCHO concentration is 9-10 mL.L -1 The concentration of NaOH is 0.01-0.02 g.mL -1 。
Further, step (5) Wherein the stirring speed of the magnetic stirrer is 300-400 r.min -1 。
Further, in the step (5), the deionized water is washed until the washing liquid is neutral.
Further, in the step (5), the vacuum drying is performed at 50-60 ℃ for 5-6 hours.
Further, the copper-plated carbon fiber is sintered and formed, and the method comprises the following steps:
and (3) pressing the copper-plated carbon fibers into a fiber felt by using a die, and placing the fiber felt in a vacuum resistance furnace for high-temperature sintering to obtain the formed copper-plated carbon fiber felt.
Further, the carbon fiber felt has a diameter of 14-15 mm and a thickness of 0.1-0.2 mm.
Still further, the sintering is performed under a hydrogen atmosphere.
Further, the sintering temperature is 750-800 ℃, and the sintering time is 60-70 min.
Further, the surface oxidation treatment of the formed copper-plated carbon fiber felt comprises the following steps:
and (3) placing the formed copper-plated carbon fiber felt in a muffle furnace, and heating and oxidizing at high temperature in an air atmosphere to obtain the carbon core/copper oxide shell composite electrode for the lithium ion battery.
Further, the temperature of the heating oxidation is 400-450 ℃ and the time is 1-2 hours.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) The nano-pore structure of the copper oxide thin layer is beneficial to the easy passing of lithium ions in electrolyte, so that the processes of lithium intercalation and lithium deintercalation occur in the carbon core, thereby increasing the charge and discharge capacity of the lithium ion battery;
(2) The carbon core/copper oxide shell composite electrode for the lithium ion battery, disclosed by the invention, has the advantages that the carbon core is in close contact with the copper oxide shell, so that the conductivity of the electrode is improved, and the volume change degree in the copper oxide conversion process is buffered;
(3) The carbon core/copper oxide shell composite electrode for the lithium ion battery, disclosed by the invention, has the advantages that the copper oxide shell tightly wraps the carbon core part, the nano needle-shaped structure of the copper oxide shell greatly shortens the diffusion distance of lithium ions, increases the effective contact area with the lithium ions, and limits the expansion of the volume of carbon fibers in the lithium intercalation and deintercalation processes of the lithium ion battery, so that the reversible capacity and the cycle life of the lithium ion battery are improved.
Drawings
FIG. 1 is a schematic view showing the overall structure of a carbon core/copper oxide shell composite electrode prepared in example 1;
FIG. 2 is a partial schematic view of the carbon core/copper oxide shell composite electrode prepared in example 1;
FIG. 3 is a schematic diagram showing the assembly of a lithium ion half-cell with a carbon core/copper oxide shell composite electrode according to example 2;
fig. 4 is a graph showing the cyclic charge and discharge test of a lithium ion half-cell equipped with a carbon core/copper oxide shell composite electrode in example 2.
Detailed Description
For a further understanding of the invention, the invention is further described below with reference to the drawings and examples, but it is to be understood that the scope of the invention claimed is not limited to the examples described and that other non-enumerated examples of parameters within the scope of the claims are equally valid.
Example 1
The preparation of the carbon core/copper oxide shell composite electrode for the lithium ion battery comprises the following steps:
preparation of copper-plated carbon fiber
(1) Surface photoresist removal: the carbon fiber with the length of 1mm is placed in the air in a high-temperature resistance furnace to be burned for 30min, the burning temperature is 400 ℃, so that the protective glue on the surface of the carbon fiber is removed, the binding force between the plating layer and the carbon fiber is improved, and the contact resistance between the plating layer and the carbon fiber is reduced;
(2) Surface roughening: placing the carbon fiber after removing the colloid in a concentration of 15wt% (NH 4 ) 2 S 2 O 8 Soaking in the solution with ultrasonic wave for 30min to obtainCoarsening and hydrophilizing the surface of the carbon fiber; then soaking the carbon fiber with 10wt% concentration NaOH solution for 5min to eliminate residual (NH) 4 ) 2 S 2 O 8 Cleaning the carbon fiber until the cleaning solution is neutral;
(3) Surface sensitization: placing the roughened carbon fiber in a catalyst consisting of SnCl 2 HCl and H 2 Sensitization solution (in sensitization solution, snCl) prepared from O 2 The concentration of (C) is 0.02 g.mL -1 HCl concentration of 40 mL.L -1 ) Soaking for 10min, and then carrying out still water rinsing on the carbon fiber for 3 times by using deionized water;
(4) Surface activation: placing the sensitized carbon fiber in a reactor consisting of AgNO 3 、NH 3 ·H 2 O and H 2 O is an activating solution (AgNO in the activating solution) 3 The concentration of (C) is 0.005 g.mL -1 ，NH 3 ·H 2 The concentration of O is 10mL.L -1 ) Soaking for 10min, and then cleaning the carbon fiber to black by deionized water;
(5) Surface copper plating: placing activated carbon fiber in NaKC 4 H 4 O 6 ·4H 2 O、CuSO 4 ·5H 2 O, HCHO, naOH and H 2 O is prepared into plating solution (NaKC in the plating solution) 4 H 4 O 6 The concentration of (C) is 0.04 g.mL -1 ，CuSO 4 The concentration of (C) is 0.01 g.mL -1 HCHO concentration of 10mL.L -1 NaOH concentration was 0.01 g/mL -1 ) In the process, a magnetic stirrer is used for 400 r.min -1 Stirring at the rotating speed until no bubbles are generated in the solution, finally washing the copper-plated carbon fiber with deionized water until the washing solution is neutral, and drying at 60 ℃ in vacuum for 6 hours to obtain the copper-plated carbon fiber.
Sintering and forming of copper-plated carbon fiber
(6) Pressing: pressing 50mg of copper-plated carbon fibers into a fiber mat with a diameter of 15mm and a thickness of 0.1 mm;
(7) Sintering: and (3) placing the pressed fiber felt in a vacuum resistance furnace, sintering at a high temperature in a hydrogen atmosphere, wherein the sintering temperature is 800 ℃, and the heat preservation time is 60 minutes, so as to obtain the formed copper-plated carbon fiber felt.
Surface oxidation treatment of formed copper-plated carbon fiber felt
(8) And (3) placing the obtained formed copper-plated carbon fiber felt in a muffle furnace, and heating and oxidizing the carbon fiber felt in the air at a high temperature of 400 ℃ for 2 hours to obtain the carbon core/copper oxide shell composite electrode for the lithium ion battery.
The overall structure schematic diagram and the partial schematic diagram of the prepared carbon core/copper oxide shell composite electrode for the lithium ion battery are respectively shown in fig. 1 and 2, and the composite electrode comprises a core part and a shell, wherein the core part is a carbon fiber 11, and the shell is a copper oxide thin layer; the copper oxide thin layer is provided with an array type nanometer needle-shaped structure 9 and a nanometer hole-shaped structure 10, the nanometer needle-shaped structure 9 is arranged on the outer surface of the copper oxide thin layer, and the nanometer hole-shaped structure 10 is a hole penetrating through the copper oxide thin layer.
Example 2
An assembly schematic diagram of the lithium ion half battery assembled by the carbon core/copper oxide shell composite electrode prepared in the embodiment 1 is shown in fig. 3, and the lithium ion half battery comprises an upper battery shell 1, a spring piece 2, a gasket 3, a lithium sheet 4, a diaphragm 5, an electrolyte 6, a lower battery shell 7 and a carbon core/copper oxide shell composite electrode 8;
the carbon core/copper oxide shell composite electrode 8 is arranged on the lower battery shell 7, the electrolyte 6 is filled with the whole cavity formed by the carbon core/copper oxide shell composite electrode 8, the lower battery shell 7 and the diaphragm 5, the whole cavity is filled with active substances, and the electrolyte 6 directly infiltrates the active substances on the carbon core/copper oxide shell composite electrode 8; the lithium sheet 4 is tightly attached to the diaphragm 5, the gasket 3 and the elastic sheet 2 are sequentially arranged on the upper surface of the lithium sheet 4 from bottom to top, the gasket 3 and the elastic sheet 2 play a role in adjusting pressure, the elastic sheet 2 is tightly contacted with the upper battery shell 1 to reduce contact resistance, and good conductivity inside the battery is ensured.
After the assembly of the lithium ion half battery is completed, lithium ions start to be removed from the lithium sheet 4 during discharging, the lithium ions enter the electrolyte 6 through the diaphragm 5 and then contact with active substances on the carbon core/copper oxide shell composite electrode 8 to be converted, and the lithium ions are directly converted with the lithium ion half battery 9 through the electrolyte and pass through the nano structure 10 to be subjected to a lithium intercalation process with the lithium ion half battery 11; meanwhile, electrons enter the lower battery shell 7 through the gasket 3, the elastic sheet 2 and the upper battery shell 1 in sequence, and as the lower battery shell 7 is in close contact with the carbon core/copper oxide shell composite electrode 8, the electrons enter the active material of the carbon core/copper oxide shell composite electrode 8 to be subjected to charge neutralization with lithium ions, so that the discharging process of the lithium ion half battery is completed; and the charging process of the lithium ion half-cell is just opposite.
In the charge and discharge process of the lithium ion half battery, the nano needle-shaped structure of the copper oxide shell greatly shortens the diffusion distance of lithium ions and increases the effective contact area between the copper oxide shell and the lithium ions, so that the reversible capacity of the battery can be greatly improved. In addition, the nano-pore structure of the copper oxide is beneficial to the easy passing of lithium ions in the electrolyte, so that the processes of lithium intercalation and lithium deintercalation occur in the carbon core, and the charge and discharge capacity of the battery is increased. In the cyclic charge and discharge process of the battery, the carbon core part is tightly contacted with the copper oxide shell, so that the conductivity of the electrode is improved, and the volume change degree in the copper oxide conversion process is buffered; the copper oxide shell tightly wraps the carbon core part, so that the volume change of the carbon core in the lithium intercalation and deintercalation process is limited to a certain extent, and the reversible capacity and the cycle life of the battery are improved.
The assembled lithium ion half-cell was subjected to a cyclic charge and discharge test using the LAND cell test system CT2001A, and the resulting test curve is shown in fig. 4. As can be seen from the graph, the lithium ion battery with the carbon core/copper oxide shell composite electrode (CuO-CF) has higher reversible capacity and better rate capability than the lithium ion battery with the copper oxide electrode (CuO) alone and the carbon fiber electrode (CF) alone. The reversible specific capacity of the lithium ion battery with the carbon core/copper oxide shell composite electrode under the current condition of 0.1C is as high as 671.2mAh/g, which is far higher than that of the lithium ion battery with the copper oxide electrode and the carbon fiber electrode. Under the condition of different multiplying powers, the reversible capacity of the lithium ion battery with the carbon core/copper oxide shell composite electrode is also very advantageous compared with other two batteries. In addition, after 0.1C, 0.2C, 0.5C, 1C and 2C multiplying power charge and discharge, the reversible capacity of the lithium ion battery with the carbon core/copper oxide shell composite electrode is still kept at 637.4 mAh/g under the current condition of 0.1C, and the reversible capacity accounts for 94.8% of the stable capacity of the battery before multiplying power charge and discharge, and the result shows that the carbon core/copper oxide shell composite electrode can effectively improve various electrochemical performances of the lithium ion battery.
The above examples of the present invention are merely illustrative of the present invention and are not intended to limit the embodiments of the present invention. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.

Claims (2)

1. The preparation method of the carbon core/copper oxide shell composite electrode for the lithium ion battery is characterized by comprising the steps of preparing copper-plated carbon fibers, sintering and forming the copper-plated carbon fibers and carrying out surface oxidation treatment on a formed copper-plated carbon fiber felt;
the preparation of the copper-plated carbon fiber comprises the following steps:
(1) Surface photoresist removal: burning the carbon fiber in the air in a high-temperature resistance furnace to remove the protective adhesive on the surface of the carbon fiber; the firing is carried out at 400-500 ℃ for 30-40 min; the length of the carbon fiber is 1-2 mm;
(2) Surface roughening: placing the burnt carbon fiber in (NH) 4 ) 2 S 2 O 8 Soaking in solution with ultrasonic wave, soaking in NaOH solution, and removing residual (NH) on the surface of carbon fiber 4 ) 2 S 2 O 8 Cleaning with deionized water; the concentration of the (NH 4) 2S2O8 solution is 15-17 wt%, the ultrasonic soaking time in the (NH 4) 2S2O8 solution is 30-40 min, the concentration of the NaOH solution is 9-11 wt%, the soaking time in the NaOH solution is 5-10 min, and the deionized water cleaning is carried out until the cleaning solution is neutral;
(3) Surface sensitization: placing the roughened carbon fiber in a catalyst consisting of SnCl 2 HCl and H 2 Soaking in sensitization solution prepared from O, and then carrying out static treatment with deionized waterRinsing with water; the said catalyst is prepared from SnCl 2 HCl and H 2 In the sensitized liquid prepared by O, snCl 2 The concentration of (C) is 0.01-0.02 g.mL -1 HCl concentration of 38-40 mL.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The soaking time is 5-10 min, and the number of times of still water rinsing is 3-4;
(4) Surface activation: placing the sensitized carbon fiber in a reactor consisting of AgNO 3 、NH 3 ·H 2 O and H 2 Soaking in an activating solution prepared by O, and then cleaning the carbon fiber to black by deionized water; the said agent is prepared from AgNO 3 、NH 3 ·H 2 O and H 2 In the activating solution prepared by O, agNO 3 The concentration of (C) is 0.004-0.005 g/mL -1 、NH 3 The concentration of (C) is 9-10 mL.L -1 The method comprises the steps of carrying out a first treatment on the surface of the The soaking time is 5-10 min;
(5) Surface copper plating: placing activated carbon fiber in NaKC 4 H 4 O 6 ·4H 2 O、CuSO 4 ·5H 2 O, HCHO, naOH and H 2 In the plating solution prepared by O, stirring by a magnetic stirrer until no bubbles are generated in the solution, and finally cleaning by deionized water and vacuum drying to obtain the copper-plated carbon fiber; the NaKC is used for preparing the 4 H 4 O 6 ·4H 2 O、CuSO 4 ·5H 2 O, HCHO, naOH and H 2 In the plating solution prepared by O, naKC 4 H 4 O 6 The concentration of (C) is 0.04-0.05 g.mL-1, cuSO 4 The concentration of (C) is 0.01-0.02 g.multidot.mL-1, and the concentration of HCHO is 9-10 mL.multidot.L -1 The concentration of NaOH is 0.01-0.02 g.multidot.mL -1 The method comprises the steps of carrying out a first treatment on the surface of the The stirring rotating speed of the magnetic stirrer is 300-400 r.min -1 The method comprises the steps of carrying out a first treatment on the surface of the The deionized water is cleaned until the cleaning solution is neutral; the vacuum drying is carried out for 5-6 hours at 50-60 ℃;
the sintering and forming of the copper-plated carbon fiber comprises the following steps:
pressing the copper-plated carbon fibers into a fiber felt by using a die, and placing the fiber felt in a vacuum resistance furnace for high-temperature sintering to obtain a formed copper-plated carbon fiber felt; the diameter of the copper-plated carbon fiber felt is 14-15 mm, and the thickness of the copper-plated carbon fiber felt is 0.1-0.2 mm; the sintering is performed under a hydrogen atmosphere; the sintering temperature is 750-800 ℃, and the sintering time is 60-70 min;
the surface oxidation treatment of the formed copper-plated carbon fiber felt comprises the following steps:
placing the formed copper-plated carbon fiber felt in a muffle furnace, and heating and oxidizing at high temperature in an air atmosphere to obtain the carbon core/copper oxide shell composite electrode for the lithium ion battery; the temperature of the heating oxidation is 400-450 ℃ and the time is 1-2 hours; the core part of the carbon core/copper oxide shell composite electrode is carbon fiber, and the shell is a copper oxide thin layer; the copper oxide thin layer has an array needle-shaped structure and a hole-shaped structure; the needle-shaped structures and the hole-shaped structures are nano-scale structures; the needle-shaped structures are arranged on the outer surface of the copper oxide thin layer, and the hole-shaped structures are holes penetrating through the copper oxide thin layer.
2. The carbon core/copper oxide shell composite electrode for a lithium ion battery, which is prepared by the preparation method of claim 1, is characterized in that the core part of the carbon core/copper oxide shell composite electrode is carbon fiber, and the shell is a copper oxide thin layer; the copper oxide thin layer has an array needle-shaped structure and a hole-shaped structure; the needle-shaped structures and the hole-shaped structures are nano-scale structures; the needle-shaped structures are arranged on the outer surface of the copper oxide thin layer, and the hole-shaped structures are holes penetrating through the copper oxide thin layer.
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