CN105895951A - Preparation method for silicon carbide coated copper-tin alloy nanoparticle composite material - Google Patents

Preparation method for silicon carbide coated copper-tin alloy nanoparticle composite material Download PDF

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CN105895951A
CN105895951A CN201610306231.4A CN201610306231A CN105895951A CN 105895951 A CN105895951 A CN 105895951A CN 201610306231 A CN201610306231 A CN 201610306231A CN 105895951 A CN105895951 A CN 105895951A
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alloy
silicon carbide
carborundum
aqueous solution
malic acid
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周荣
孟浩影
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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
    • 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
    • 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
    • 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
    • H01M4/387—Tin or alloys based on tin
    • 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
    • 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
    • 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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Abstract

The invention discloses a preparation method for a silicon carbide coated copper-tin alloy nanoparticle composite material, belonging to the technical field of electrochemistry. The preparation method comprises the following steps of firstly, taking alloy nanoparticle Cu6Sn5 as a body, reducing a CuCl2/SnCl4 solution by a NaBH4 reduction agent, adding malic acid as a complexing agent so as to effectively prevent the alloy nanoparticle from growing and obtain nanoscale alloy particle; synthesizing silicon carbide by taking sucrose, tetraethyl orthosilicate and organic silicon as raw materials, grinding the silicon carbide and the nanometer alloy particle, and carrying out high-temperature calcination to obtain the silicon carbide coated alloy nanoparticle composite material. By coating the alloy with the silicon carbide with a low expansion coefficient, the volume change of the nanometer alloy particle is very low during the charging-discharging process, and the problems of secondary agglomeration of the nanometer particles, gradually-growing particles and pulverization and peeling phenomena to reduce the performance of the electrode material are solved. The method is simple and easy to operate.

Description

A kind of preparation method of carborundum coated copper ashbury metal nano composition
Technical field
The invention discloses the preparation method of a kind of carborundum coated copper ashbury metal nano composition, belong to technical field of electrochemistry.
Background technology
Along with economic development, necessarily cause increasing the weight of of the depletion of natural resources such as oil, coal, environmental pollution and global greenhouse effect.The mankind must hold the equilibrium relation between economic growth, environmental conservation and energy resource supply this Trinitarian " three E ".The consumption figure that the energy is annual in the world now is converted to oil and is about 8,000,000,000 tons, and wherein 90% is Fossil fuel.By present consumption rate, about will be exhausted after 100 years to 200 years.The comprehensive high-efficiency development and utilization of new forms of energy, power-saving technology and green technology, it has also become the most urgent problem.Lithium ion battery, as a kind of newer secondary energy sources, applies in the middle of daily life the most widely.But being as the development of science and technology, current business-like lithium ion battery is had higher requirement by people, it is desirable to be able to improve its power density and energy density further.For current business-like graphite material, its theoretical capacity only has 372mAh/g, is increasingly difficult to meet the demand of the various electronic products the most perfect along with scientific and technological progress.Therefore, lithium ion battery industry will be brought revolutionary development by a kind of negative material with suitable potential and high power capacity.
In recent years, research finds that many metals (Sn, Zn, Al, Si etc.) can form alloy therewith with embedding lithium, and its theoretical embedding lithium capacity is significantly larger than graphite material.But, there is serious volumetric expansion and contraction in these materials during intercalation/deintercalation lithium, is easily caused avalanche and the efflorescence of electrode material, the peeling phenomenon of material structure, and this allows for material and i.e. fluid loose contact, and the cycle performance of electrode drastically declines.Development along with scientific research, it has been found that the alloy material of some binary can also embedding lithium, and its chemical property is better than the alloy material of unitary.1999, American Studies personnel found Cu6Sn5Alloy material can embed Li ion and form LixCu6Sn5Alloy, the theoretical capacity of embedding lithium can reach 650mAh/g, is far longer than the theoretical capacity of graphite, and its energy density per unit volume metric density than graphite big several times, is a kind of up-and-coming energy-density lithium ion battery negative material simultaneously.Calendar year 2001, the research worker of Korea S have studied the Mg synthesized by mechanical ball milling method2The chemical property of Sn alloy and removal lithium embedded mechanism.Result shows that its reversible capacity reaches 400mAh/g, circulates and still has bigger reversible capacity 20 times.In binary system alloy, inactive metal (such as Mg, Ni, Cu) plays dispersion buffer medium effect in lattice, reduces volumetric expansion when lithium embeds and deviates from, and therefore the cycle performance of bianry alloy is higher than unitary alloy.While it is true, the binary alloy material of common synthesis is owing to yet suffering from the pulverizing problem of volumetric expansion and electrode material in process of intercalation, its performance is unable to reach business-like requirement.Research finds, prepares nano level alloy material and can reduce its absolute volume change in charge and discharge process, has more preferable cycle performance than common alloy material.The most nano level alloy material, the volumetric expansion in cyclic process will also result in the secondary agglomeration of nanoparticle, and granule occurs again efflorescence peeling phenomenon after gradually growing up thus reduces the performance of electrode material.
Summary of the invention
The technical problem that present invention mainly solves: cause nanoparticle secondary agglomeration for current nanoscale alloy material volumetric expansion during cycle charge-discharge, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material, providing the preparation method of a kind of carborundum coated copper ashbury metal nano composition, first the present invention is with alloy nano particle Cu6Sn5For body, pass through NaBH4Also original reagent reduction CuCl2 /SnCl4Solution, add malic acid as chelating agent, growing up of effective suppression alloying pellet, thus obtain nano level alloy particle, then with sucrose, tetraethyl orthosilicate, organosilicon is Material synthesis carborundum, carborundum is ground with Nanoalloy particle, carborundum clad alloy nano composition is obtained after high-temperature calcination, the present invention is by by low-expansion carborundum clad alloy, make Nanoalloy particle change in volume in charge and discharge process the least, solve the secondary agglomeration of nanoparticle, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material, the present invention is simple to operate, easily operated.
In order to solve above-mentioned technical problem, the technical solution adopted in the present invention is:
(1) 2～3g malic acids and 6～8gNaBH are weighed respectively4Join in the 1000mL beaker filling 500～600mL deionized waters, with 180～200W ultrasonic echography concussions 5～10min, obtain malic acid/NaBH4Aqueous solution；
(2) 2～4gCuCl are weighed2With 6～8gSnCl4Join in the 500mL beaker filling 200～300mL deionized waters, stir 5～10min, dissolve, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 5～10mL/min while stirring4In aqueous solution, after dropping, stirring reaction 30～40min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 3～5 times, the filtering residue after washing is put into vacuum drying oven, is dried 2～3h, obtains Nanoalloy particle Cu6Sn5, standby；
(3) weigh 10～20g sucrose and join in the 1000mL beaker filling 500～600mL deionized waters, add in beaker again and enter 20～30g tetraethyl orthosilicates, 2～4g organosilicon, 2～4g malic acid successively, temperature controlled water baths is at 50～60 DEG C, stirring reaction 10～12h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 180～200 DEG C of baking ovens 12～14h, obtains carborundum；
(4) by Nanoalloy particle Cu standby in above-mentioned carborundum and step (2)6Sn5Being placed in ball mill and grind 5～6h with rotating speed 400～500r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 7～8h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 700～800 DEG C.
The method of the application of the present invention: weigh the carborundum clad alloy nano composition that the 0.1～0.3g present invention prepares respectively and put in the beaker equipped with 30～50mL dehydrated alcohol, again successively by 1～3g conductive black and 0.5～0.7g politef in beaker, stirring is mixed and made into negative material, the negative material prepared by alloy is assembled into battery, the capacity when discharging first of battery has reached more than 800mAh/g, it is significantly larger than the capacity of lithium battery on the market, after discharge and recharge 30 times, capacity is more than 400mAh/g.
The invention has the beneficial effects as follows:
(1) present invention is by by low-expansion carborundum clad alloy, make Nanoalloy particle change in volume in charge and discharge process the least, solving the secondary agglomeration of nanoparticle, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material；
(2) present invention is the most simple to operate, and the charge/discharge capacity of material have also been obtained increase.
Detailed description of the invention
Weigh 2～3g malic acids and 6～8gNaBH the most respectively4Join in the 1000mL beaker filling 500～600mL deionized waters, with 180～200W ultrasonic echography concussions 5～10min, obtain malic acid/NaBH4Aqueous solution；Weigh 2～4gCuCl2With 6～8gSnCl4Join in the 500mL beaker filling 200～300mL deionized waters, stir 5～10min, dissolve, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 5～10mL/min while stirring4In aqueous solution, after dropping, stirring reaction 30～40min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 3～5 times, the filtering residue after washing is put into vacuum drying oven, is dried 2～3h, obtains Nanoalloy particle Cu6Sn5, standby；Weigh 10～20g sucrose and join in the 1000mL beaker filling 500～600mL deionized waters, add in beaker again and enter 20～30g tetraethyl orthosilicates, 2～4g organosilicon, 2～4g malic acid successively, temperature controlled water baths is at 50～60 DEG C, stirring reaction 10～12h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 180～200 DEG C of baking ovens 12～14h, obtains carborundum；By above-mentioned carborundum and standby Nanoalloy particle Cu6Sn5Being placed in ball mill and grind 5～6h with rotating speed 400～500r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 7～8h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 700～800 DEG C.
Example 1
Weigh 2g malic acid and 6gNaBH the most respectively4Join in the 1000mL beaker filling 500mL deionized water, shake 5min with 180W ultrasonic echography, obtain malic acid/NaBH4Aqueous solution；Weigh 2gCuCl2And 6gSnCl4Join in the 500mL beaker filling 200mL deionized water, stir 5min, dissolve, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 5mL/min while stirring4In aqueous solution, after dropping, stirring reaction 30min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 3 times, the filtering residue after washing is put into vacuum drying oven, is dried 2h, obtains Nanoalloy particle Cu6Sn5, standby；Weigh 10g sucrose and join in the 1000mL beaker filling 500mL deionized water, add in beaker again and enter 20g tetraethyl orthosilicate, 2g organosilicon, 2g malic acid successively, temperature controlled water baths is at 50 DEG C, stirring reaction 10h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 180 DEG C of baking ovens 12h, obtains carborundum；By above-mentioned carborundum and standby Nanoalloy particle Cu6Sn5Being placed in ball mill and grind 5h with rotating speed 400r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 7h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 700 DEG C.
Weigh the carborundum clad alloy nano composition that the 0.1g present invention prepares and put in the beaker equipped with 30mL dehydrated alcohol, again successively by 1g conductive black and 0.5g politef in beaker, stirring is mixed and made into negative material, the negative material prepared by alloy is assembled into battery, the capacity when discharging first of battery has reached 810mAh/g, being significantly larger than the capacity of lithium battery the most on the market, after discharge and recharge 30 times, capacity is 420mAh/g；The present invention is by by low-expansion carborundum clad alloy, make Nanoalloy particle change in volume in charge and discharge process the least, solving the secondary agglomeration of nanoparticle, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material；The present invention is the most simple to operate, and the charge/discharge capacity of material have also been obtained increase.
Example 2
Weigh 2.5g malic acid and 7gNaBH the most respectively4Join in the 1000mL beaker filling 550mL deionized water, shake 8min with 190W ultrasonic echography, obtain malic acid/NaBH4Aqueous solution；Weigh 2～4gCuCl2And 7gSnCl4Join in the 500mL beaker filling 250mL deionized water, stir 8min, dissolve, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 8mL/min while stirring4In aqueous solution, after dropping, stirring reaction 35min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 4 times, the filtering residue after washing is put into vacuum drying oven, is dried 2.5h, obtains Nanoalloy particle Cu6Sn5, standby；Weigh 15g sucrose and join in the 1000mL beaker filling 550mL deionized water, add in beaker again and enter 25g tetraethyl orthosilicate, 23g organosilicon, 3g malic acid successively, temperature controlled water baths is at 55 DEG C, stirring reaction 11h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 190 DEG C of baking ovens 13h, obtains carborundum；By above-mentioned carborundum and standby Nanoalloy particle Cu6Sn5Being placed in ball mill and grind 5.5h with rotating speed 450r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 7.5h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 750 DEG C.
Weigh the carborundum clad alloy nano composition that the 0.2g present invention prepares and put in the beaker equipped with 40mL dehydrated alcohol, again successively by 2g conductive black and 0.6g politef in beaker, stirring is mixed and made into negative material, the negative material prepared by alloy is assembled into battery, the capacity when discharging first of battery has reached 830mAh/g, being significantly larger than the capacity of lithium battery the most on the market, after discharge and recharge 30 times, capacity is 450mAh/g；The present invention is by by low-expansion carborundum clad alloy, make Nanoalloy particle change in volume in charge and discharge process the least, solving the secondary agglomeration of nanoparticle, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material；The present invention is the most simple to operate, and the charge/discharge capacity of material have also been obtained increase.
Example 3
Weigh 3g malic acid and 8gNaBH the most respectively4Join in the 1000mL beaker filling 600mL deionized water, shake 10min with 200W ultrasonic echography, obtain malic acid/NaBH4Aqueous solution；Weigh 4gCuCl2And 8gSnCl4Join in the 500mL beaker filling 300mL deionized water, stir 10min, dissolve, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 10mL/min while stirring4In aqueous solution, after dropping, stirring reaction 40min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 5 times, the filtering residue after washing is put into vacuum drying oven, is dried 3h, obtains Nanoalloy particle Cu6Sn5, standby；Weigh 20g sucrose and join in the 1000mL beaker filling 600mL deionized water, add in beaker again and enter 30g tetraethyl orthosilicate, 4g organosilicon, 4g malic acid successively, temperature controlled water baths is at 60 DEG C, stirring reaction 12h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 200 DEG C of baking ovens 14h, obtains carborundum；By above-mentioned carborundum and standby Nanoalloy particle Cu6Sn5Being placed in ball mill and grind 6h with rotating speed 500r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 8h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 800 DEG C.
Weigh the carborundum clad alloy nano composition that the 0.3g present invention prepares and put in the beaker equipped with 50mL dehydrated alcohol, again successively by 3g conductive black and 0.7g politef in beaker, stirring is mixed and made into negative material, the negative material prepared by alloy is assembled into battery, the capacity when discharging first of battery has reached 850mAh/g, being significantly larger than the capacity of lithium battery the most on the market, after discharge and recharge 30 times, capacity is 470mAh/g；The present invention is by by low-expansion carborundum clad alloy, make Nanoalloy particle change in volume in charge and discharge process the least, solving the secondary agglomeration of nanoparticle, granule is gradually grown up and efflorescence peeling phenomenon occurs thus the problem that reduces the performance of electrode material；The present invention is the most simple to operate, and the charge/discharge capacity of material have also been obtained increase.

Claims (1)

1. the preparation method of a carborundum coated copper ashbury metal nano composition, it is characterised in that concrete preparation process is:
(1) 2～3g malic acids and 6～8gNaBH are weighed respectively4Join in the 1000mL beaker filling 500～600mL deionized waters, with 180～200W ultrasonic echography concussions 5～10min, obtain malic acid/NaBH4Aqueous solution；
(2) 2～4gCuCl are weighed2With 6～8gSnCl4Join in the 500mL beaker filling 200～300mL deionized waters, stirring 5～10min dissolving, obtain CuCl2/ SnCl4Aqueous solution, by CuCl2/ SnCl4Aqueous solution is added drop-wise to above-mentioned malic acid/NaBH with 5～10mL/min while stirring4In aqueous solution, after dropping, stirring reaction 30～40min, by reacting liquid filtering, obtains filtering residue, is washed with deionized by filtering residue 3～5 times, the filtering residue after washing is put into vacuum drying oven, is dried 2～3h, obtains Nanoalloy particle Cu6Sn5, standby；
(3) weigh 10～20g sucrose and join in the 1000mL beaker filling 500～600mL deionized waters, add in beaker again and enter 20～30g tetraethyl orthosilicates, 2～4g organosilicon, 2～4g malic acid successively, temperature controlled water baths is at 50～60 DEG C, stirring reaction 10～12h, prepare carbon silicon binary colloidal sol, colloidal sol is dried in 180～200 DEG C of baking ovens 12～14h, obtains carborundum；
(4) by Nanoalloy particle Cu standby in above-mentioned carborundum and step (2)6Sn5Being placed in ball mill and grind 5～6h with rotating speed 400～500r/min, cross 200 mesh sieves, powder body grinding obtained is put in Muffle furnace, calcines 7～8h, naturally cool to room temperature, obtain carborundum coated copper ashbury metal nano composition at 700～800 DEG C.
CN201610306231.4A 2016-05-10 2016-05-10 Preparation method for silicon carbide coated copper-tin alloy nanoparticle composite material Withdrawn CN105895951A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106601996A (en) * 2017-01-19 2017-04-26 华南理工大学 Multilayer nano-composite electrode for lithium ion battery and preparation method thereof
CN107799723A (en) * 2016-08-30 2018-03-13 华为技术有限公司 A kind of silicon substrate composite negative plate and preparation method thereof and lithium rechargeable battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107799723A (en) * 2016-08-30 2018-03-13 华为技术有限公司 A kind of silicon substrate composite negative plate and preparation method thereof and lithium rechargeable battery
CN106601996A (en) * 2017-01-19 2017-04-26 华南理工大学 Multilayer nano-composite electrode for lithium ion battery and preparation method thereof
CN106601996B (en) * 2017-01-19 2023-11-21 华南理工大学 Multilayer nano composite electrode for lithium ion battery and preparation method thereof

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