CN103887494A - Method for preparing copper phosphide/copper composite material and application of copper phosphide/copper composite material in lithium ion battery - Google Patents

Method for preparing copper phosphide/copper composite material and application of copper phosphide/copper composite material in lithium ion battery Download PDF

Info

Publication number
CN103887494A
CN103887494A CN201410085468.5A CN201410085468A CN103887494A CN 103887494 A CN103887494 A CN 103887494A CN 201410085468 A CN201410085468 A CN 201410085468A CN 103887494 A CN103887494 A CN 103887494A
Authority
CN
China
Prior art keywords
copper
phosphide
carbon
composite material
foam
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410085468.5A
Other languages
Chinese (zh)
Other versions
CN103887494B (en
Inventor
倪世兵
马建军
吕小虎
杨学林
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
CHONGQING JIABAOCHENG ENERGY TECHNOLOGY CO., LTD.
Original Assignee
China Three Gorges University CTGU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by China Three Gorges University CTGU filed Critical China Three Gorges University CTGU
Priority to CN201410085468.5A priority Critical patent/CN103887494B/en
Publication of CN103887494A publication Critical patent/CN103887494A/en
Application granted granted Critical
Publication of CN103887494B publication Critical patent/CN103887494B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/049—Manufacturing of an active layer by chemical means
    • H01M4/0497—Chemical precipitation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/5805—Phosphides
    • 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
    • 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 provides a method for preparing a copper phosphide/copper composite material. The method comprises the following steps: by taking red phosphorus and foamy copper as basic raw materials, sequentially paving the red phosphorus and the foamy copper in a ceramic boat from bottom to top, and preparing the composite material under nitrogen protection by adopting a gas-solid reaction method. Copper phosphide uniformly grows on the surface of foamy copper, has a porous structure and has the average particle size being 300-500nm. The copper phosphide/copper composite material prepared by the method serving as an anode material is applied to a lithium ion battery, the first charge capacity and the first discharge capacity are respectively 400mAh/g and 341mAh/g, and the charge capacity and the discharge capacity are respectively 409mAh/g and 398mAh/g after cycling for 60 times. According to the method, the process is simple, the operation is easy, the material preparation cost is low, the reaction process belongs to a gas-solid reaction, the reaction raw materials are fully contacted, the reaction is full, and residual phosphorus on a conductive matrix is avoided.

Description

A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery
Technical field
The present invention relates to a class Novel cathode material for lithium ion battery, particularly a kind of preparation method of porous copper phosphide/carbon/carbon-copper composite material and storage lithium characteristic thereof, belong to field of electrochemical power source.
Background technology
Based on a kind of special oxidation/reduction reaction mechanism, transition group metallic oxide has the theoretical specific capacity far above graphite as Novel cathode material for lithium ion battery, has potential using value in lithium ion battery.This type of mechanism is not only applicable to transition group metallic oxide, and is applicable to sulfide, nitride, fluoride, phosphide etc.In oxidation/reduction type negative material, phosphide has relatively low charge and discharge platform, and positive electrode coupling has higher voltage while using, is conducive to improve the power density of lithium ion battery.In addition, the charge and discharge platform stable of phosphide, can provide stable Voltage-output as lithium ion battery negative material.But the same with other oxidation/reduction type negative materials, phosphide conductivity is poor, there will be the destruction of initial configuration and pattern in cyclic process, causes cyclical stability poor.Phosphide growth in situ is not only conducive to improve on conducting base its electric conductivity, can also strengthens its structural stability, thereby improve its chemical property.Existing method, by first red phosphorus being distributed on Copper Foil or copper coin, is then passed through high temperature solid state reaction, thereon growth in situ copper phosphide in 250 ~ 400 degree scopes under protective gas condition.Because red phosphorus directly contacts with copper matrix, react more violent, process is difficult to control, and the copper phosphide uniformity generating is poor, and has reacted easily and be bonded with the not red phosphorus of complete reaction at copper matrix surface.In addition, because the specific area of Copper Foil or copper sheet is less, copper phosphide/the copper compound structure obtaining is unfavorable for fully contacting of electrolyte and copper phosphide when the lithium ion battery negative material, and along with the increase of copper phosphide quality, copper phosphide/copper compound structure conductivity worsens rapidly, thereby causes chemical property undesirable.Therefore, the key of research and development high performance lithium ionic cell cathode material copper phosphide/copper is to prepare copper phosphide and evenly grows, is conducive to the composite construction that electrolyte fully contacts with copper phosphide.Foam copper has three-dimensional porous structure, good electric conductivity and structural stability, specific area is far above Copper Foil and copper sheet, in lithium ion battery, not only can be used as conductive filling material, also can be used as conducting base in-situ deposition, grown silicon, tin and metal oxide materials, shown good chemical property using it as lithium ion battery negative material.Using three-dimensional porous foam copper as conducting base, growth in situ copper phosphide material thereon, not only be conducive to contacting of electrolyte and copper phosphide, the three-dimensional porous structure of foam copper also will effectively cushion the change in volume of copper phosphide in cyclic process, the structural stability of reinforcing material, thus its chemical property improved.At present, on foam copper, the research of growth in situ copper phosphide there is not yet report.Based on above research background, this patent is invented a kind of gas-solid reaction method and is prepared the copper phosphide/carbon/carbon-copper composite material of copper phosphide uniform deposition on foam copper surface, the copper phosphide depositing is loose structure, has shown excellent cyclical stability using it as lithium ion battery negative.
Summary of the invention
Object of the present invention is exactly to prepare the copper phosphide/carbon/carbon-copper composite material of loose structure by gas-solid reaction taking red phosphorus and foam copper as the basic raw material of reaction, by gasification phosphorus uniform deposition on foam copper, form high performance lithium ion battery composite negative pole material, wherein the mass ratio of red phosphorus and foam copper is 1:5 ~ 1:10.Its principle utilizes high-temperature heating that first red phosphorus gasified exactly, and the red phosphorus after gasification and foam copper (are bought in Changsha Liyuan New Material Co., Ltd. bore hole size 200 ~ 500 mm, surface density 380 g/m 2, thickness 1.5 mm) fully contact concurrent biochemical reaction, the uniform porous copper phosphide of finally directly growing on foam copper.
The synthesis material of copper phosphide/carbon/carbon-copper composite material involved in the present invention is foam copper and red phosphorus, and the reaction occurring in course of reaction is:
P (s) →P (g) (1)
P (g) + 3Cu → Cu 3P (2)
In material preparation process, first appropriate red phosphorus is ground and is laid in ceramic boat, tiling thickness is 1 ~ 3mm, and foam copper is positioned over.Between foam copper and red phosphorus, separate with foam copper fines, avoid foam copper directly to contact with red phosphorus and vigorous reaction at high temperature occurs.Described red phosphorus tiling thickness is 1.0 ~ 3.0mm, and foam copper fines is of a size of 1 ~ 3mm, and foam copper fines thickness is 0.5 ~ 1.0mm, and foam copper tiling thickness is 0.5 ~ 1.5mm, foam copper aperture size 200 ~ 500mm.
Then ceramic boat is placed in heating container, under condition of nitrogen gas, is heated to 300 ~ 400 degree reaction 1 ~ 10 hour, make the red phosphorus after gasification fully contact concurrent biochemical reaction with foam copper, the naturally cooling copper phosphide/carbon/carbon-copper composite material that obtains.
Copper phosphide/the carbon/carbon-copper composite material that adopts the method to prepare is loose structure, and copper phosphide is evenly grown in foam copper surface, and particle mean size is 300 ~ 500 nm.
Copper phosphide/the carbon/carbon-copper composite material that adopts the method to prepare is applied in lithium ion battery as negative material, and charge and discharge capacity is respectively 400,341 mAh/g first, and after 60 circulations, charge and discharge capacity is respectively 409,398 mAh/g.
Copper phosphide/copper negative material and preparation method involved in the present invention have the following advantages:
(1) synthesis technique is simple, easy operating, and material preparation cost is low;
(2) course of reaction belongs to a kind of gas-solid reaction, and reaction raw materials contact fully, reacts completely, and avoids residual phosphorus on conducting base;
(3) copper phosphide layer is evenly distributed on foam copper surface, is loose structure;
(4) prepared material charge and discharge platform stable, voltage polarizing is little, and capacity is higher, cycle performance excellence.
brief description of the drawings:
The XRD collection of illustrative plates of Fig. 1 embodiment 1 prepared sample.
The SEM figure of Fig. 2 embodiment 1.
First three of Fig. 3 embodiment 1 time charge and discharge curve (a) and cycle performance figure (b).
The XRD collection of illustrative plates of Fig. 4 embodiment 2 prepared samples.
First three of Fig. 5 embodiment 2 time charge and discharge curve (a) and cycle performance figure (b).
The XRD collection of illustrative plates of Fig. 6 embodiment 3 prepared samples.
First three of Fig. 7 embodiment 3 time charge and discharge curve (a) and cycle performance figure (b).
embodiment:
embodiment 1
Take 1g red phosphorus, in mortar, grind 10 minutes, be transferred in ceramic boat and tile, then foam copper (long 4.8 centimetres, wide 2.4 centimetres, 5) is stacked on red phosphorus, between foam copper and red phosphorus, separate with foam copper fines, avoid direct contact.Ceramic boat is moved in high temperature process furnances, under 350 DEG C of conditions, calcine in nitrogen 5 hours, naturally coolingly can obtain required sample.Result shows, prepared sample is copper phosphide/carbon/carbon-copper composite material (as shown in Figure 1) through XRD atlas analysis, is positioned at 44.4 °, 51.7 ° and 76.4 in figure odiffraction maximum corresponding to (111) of fcc Cu, (200) and (220) crystal face.Be positioned at 36.0 °, 39.0 °, 41.6 °, (112) of 45.1 ° and 46.1 ° of diffraction maximums of locating and hexagonal crystal system copper phosphide, (202), (121), (300) and (113) crystal face correspondence, lattice constant is a=0.6954 nm, c=0.7149 nm, corresponding to XRD card JCPDS, No. 65-3628.Prepared copper phosphide/copper scans through SEM, and as seen from Figure 2, copper phosphide is evenly grown in foam copper surface, is loose structure, and the particle that is 500 nm by a large amount of average grain diameters forms.Stable charge and discharge platform and less voltage polarizing have been shown using prepared copper phosphide/copper as lithium ion battery negative material, charge and discharge capacity is 325,450 mAh/g first, after 60 circulations, charge and discharge capacity is respectively 383,395 mAh/g, has shown fabulous stable circulation performance (as shown in Figure 3).
embodiment 2
Take 1g red phosphorus, in mortar, grind 10 minutes, be transferred in ceramic boat and tile, then foam copper (long 4.8 centimetres, wide 2.4 centimetres, 5) is stacked on red phosphorus, between foam copper and red phosphorus, separate with foam copper fines, avoid direct contact.Ceramic boat is moved in high temperature process furnances, under 300 DEG C of conditions, calcine in nitrogen 5 hours, naturally coolingly can obtain required sample.Result shows, prepared sample is copper phosphide/carbon/carbon-copper composite material through XRD atlas analysis, is positioned at 44.4 °, 51.7 ° and 76.4 in figure odiffraction maximum corresponding to (111) of fcc Cu, (200) and (220) crystal face.Be positioned at 45.1 ° and 46.1 ° of diffraction maximums of locating corresponding with (300) and (113) crystal face of hexagonal crystal system copper phosphide, lattice constant is a=0.6954 nm, c=0.7149 nm, corresponding to XRD card JCPDS, No. 65-3628 (as shown in Figure 4).Stable charge and discharge platform and less voltage polarizing have been shown using prepared copper phosphide/copper as lithium ion battery negative material, charge and discharge capacity is 313,384 mAh/g first, after 60 circulations, charge and discharge capacity is respectively 377,386 mAh/g, has shown fabulous stable circulation performance (as shown in Figure 5).
embodiment 3
Take 1g red phosphorus, in mortar, grind 10 minutes, be transferred in ceramic boat and tile, then foam copper (long 4.8 centimetres, wide 2.4 centimetres, 5) is stacked on red phosphorus, between foam copper and red phosphorus, separate with foam copper fines, avoid direct contact.Ceramic boat is moved in high temperature process furnances, under 400 DEG C of conditions, calcine in nitrogen 5 hours, naturally coolingly can obtain required sample.Result shows, prepared sample is copper phosphide/carbon/carbon-copper composite material through XRD atlas analysis, is positioned at 44.4 °, 51.7 ° and 76.4 in figure odiffraction maximum corresponding to (111) of fcc Cu, (200) and (220) crystal face.Be positioned at 36.0 °, 39.0 °, 41.6 °, (112) of 45.1 ° and 46.1 ° of diffraction maximums of locating and hexagonal crystal system copper phosphide, (202), (121), (300) and (113) crystal face correspondence, lattice constant is a=0.6954 nm, c=0.7149 nm, corresponding to XRD card JCPDS, No. 65-3628(is as shown in Figure 6).Stable charge and discharge platform and less voltage polarizing have been shown using prepared copper phosphide/copper as lithium ion battery negative material, charge and discharge capacity is 373,691 mAh/g first, after 60 circulations, charge and discharge capacity is respectively 291,302 mAh/g, has shown fabulous stable circulation performance (as shown in Figure 7).

Claims (6)

1. a preparation method for copper phosphide/carbon/carbon-copper composite material, is characterized in that: taking red phosphorus and foam copper as basic material, red phosphorus, foam copper are laid in ceramic boat from bottom to up successively, under nitrogen protection, adopt gas-solid reaction method to make.
2. the preparation method of copper phosphide/carbon/carbon-copper composite material according to claim 1, it is characterized in that: between red phosphorus and foam copper, separate with foam copper fines, wherein said red phosphorus tiling thickness is 1.0 ~ 3.0mm, foam copper fines is of a size of 1 ~ 3mm, foam copper fines thickness is 0.5 ~ 1.0mm, foam copper tiling thickness is 0.5 ~ 1.5mm, foam copper aperture size 200 ~ 500mm.
3. the preparation method of copper phosphide/carbon/carbon-copper composite material according to claim 1, is characterized in that: the mass ratio of red phosphorus and foam copper is 1:5 ~ 10.
4. the preparation method of copper phosphide/carbon/carbon-copper composite material according to claim 1, is characterized in that: under nitrogen protection, and gas-solid reaction 1 ~ 10 hour at 300 ~ 400 DEG C.
5. copper phosphide/carbon/carbon-copper composite material, is characterized in that: copper phosphide is evenly grown in foam copper surface, is loose structure, and particle mean size is 300 ~ 500 nm.
6. the application of copper phosphide/carbon/carbon-copper composite material in lithium ion battery, is characterized in that: using copper phosphide/carbon/carbon-copper composite material as lithium ion battery negative material.
CN201410085468.5A 2014-03-11 2014-03-11 A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery Expired - Fee Related CN103887494B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410085468.5A CN103887494B (en) 2014-03-11 2014-03-11 A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410085468.5A CN103887494B (en) 2014-03-11 2014-03-11 A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery

Publications (2)

Publication Number Publication Date
CN103887494A true CN103887494A (en) 2014-06-25
CN103887494B CN103887494B (en) 2015-11-11

Family

ID=50956296

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410085468.5A Expired - Fee Related CN103887494B (en) 2014-03-11 2014-03-11 A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery

Country Status (1)

Country Link
CN (1) CN103887494B (en)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104868098A (en) * 2015-05-15 2015-08-26 三峡大学 Negative electrode of carbon-composite Cu3P-Cu lithium-ion battery and preparation method of negative electrode
CN104979556A (en) * 2015-05-15 2015-10-14 三峡大学 Nitrogen-doped Cu3P/C-Cu lithium-ion battery negative electrode material and preparation method thereof
CN105024071A (en) * 2015-06-24 2015-11-04 三峡大学 Cu2S/Cu anode material for lithium ion battery and preparation method
CN104409699B (en) * 2014-11-19 2016-06-08 陕西科技大学 The preparation method of a kind of graphene coated cuprous phosphide matrix material
CN109638228A (en) * 2018-11-27 2019-04-16 扬州大学 A kind of preparation method of Hawkins cell negative electrode material
CN111313006A (en) * 2020-03-03 2020-06-19 顺德职业技术学院 Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof
CN111564610A (en) * 2020-04-03 2020-08-21 华南师范大学 Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof
CN114162803A (en) * 2021-12-07 2022-03-11 温州大学 Method for injecting phosphorus in liquid phase in hollow carbon nanospheres and red phosphorus anode material
US11764153B1 (en) 2022-07-28 2023-09-19 Chun-Ming Lin Interconnect structure and manufacturing method for the same

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11842958B2 (en) 2022-03-18 2023-12-12 Chun-Ming Lin Conductive structure including copper-phosphorous alloy and a method of manufacturing conductive structure

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002170560A (en) * 2000-09-25 2002-06-14 Sumitomo Metal Ind Ltd Negative electrode material for nonaqueous system secondary battery and method for manufacturing the same
CN1572413A (en) * 2003-05-27 2005-02-02 Ykk株式会社 Electrode material and method for manufacture thereof
US20090286156A1 (en) * 2005-05-18 2009-11-19 Frederic Gillot Method for production of an anode for a lithium-ion battery
CN103466574A (en) * 2013-09-17 2013-12-25 天津工业大学 Method for preparing three-dimensional macroporous metal phosphide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002170560A (en) * 2000-09-25 2002-06-14 Sumitomo Metal Ind Ltd Negative electrode material for nonaqueous system secondary battery and method for manufacturing the same
CN1572413A (en) * 2003-05-27 2005-02-02 Ykk株式会社 Electrode material and method for manufacture thereof
US20090286156A1 (en) * 2005-05-18 2009-11-19 Frederic Gillot Method for production of an anode for a lithium-ion battery
CN103466574A (en) * 2013-09-17 2013-12-25 天津工业大学 Method for preparing three-dimensional macroporous metal phosphide

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
LUCA DE TRIZIO ET AL: ""Size-Tunable, Hexagonal Plate-like Cu3P and Janus-like Cu-Cu3P Nanocrystals"", 《ACSNANO》, vol. 6, no. 1, 3 December 2012 (2012-12-03) *

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104409699B (en) * 2014-11-19 2016-06-08 陕西科技大学 The preparation method of a kind of graphene coated cuprous phosphide matrix material
CN104868098A (en) * 2015-05-15 2015-08-26 三峡大学 Negative electrode of carbon-composite Cu3P-Cu lithium-ion battery and preparation method of negative electrode
CN104979556A (en) * 2015-05-15 2015-10-14 三峡大学 Nitrogen-doped Cu3P/C-Cu lithium-ion battery negative electrode material and preparation method thereof
CN104868098B (en) * 2015-05-15 2018-03-27 三峡大学 A kind of carbon composite Cu3P Cu negative electrode of lithium ion battery and preparation method thereof
CN105024071A (en) * 2015-06-24 2015-11-04 三峡大学 Cu2S/Cu anode material for lithium ion battery and preparation method
CN105024071B (en) * 2015-06-24 2018-03-02 三峡大学 A kind of Cu2S/Cu lithium ion battery negative materials and preparation method
CN109638228A (en) * 2018-11-27 2019-04-16 扬州大学 A kind of preparation method of Hawkins cell negative electrode material
CN111313006A (en) * 2020-03-03 2020-06-19 顺德职业技术学院 Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof
CN111313006B (en) * 2020-03-03 2022-05-10 顺德职业技术学院 Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof
CN111564610A (en) * 2020-04-03 2020-08-21 华南师范大学 Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof
CN111564610B (en) * 2020-04-03 2021-06-08 华南师范大学 Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof
CN114162803A (en) * 2021-12-07 2022-03-11 温州大学 Method for injecting phosphorus in liquid phase in hollow carbon nanospheres and red phosphorus anode material
US11764153B1 (en) 2022-07-28 2023-09-19 Chun-Ming Lin Interconnect structure and manufacturing method for the same

Also Published As

Publication number Publication date
CN103887494B (en) 2015-11-11

Similar Documents

Publication Publication Date Title
CN103887494B (en) A kind of preparation method of copper phosphide/carbon/carbon-copper composite material and the application in lithium ion battery
Zou et al. Revealing cycling rate-dependent structure evolution in Ni-rich layered cathode materials
CN103078090B (en) Lithium ion power battery composite cathode material and its preparation method
CN104143635B (en) A kind of artificial plumbago negative pole material and preparation method thereof
CN104201363B (en) The coated Li of a kind of carbon3VO4Lithium ion battery cathode material and its preparation method
CN104659366A (en) Preparation method of anode material for power lithium ion battery
CN101924209B (en) Lithium ion battery cathode material and preparation method thereof
CN104218214B (en) A kind of lithium ion battery negative material and preparation method thereof
CN105314622A (en) Method for preparing hetero-atom doped porous carbon material through carbonation of biomass under assistance of molten salt
Sun et al. Degradation mechanism of O3-type NaNi1/3Fe1/3Mn1/3O2 cathode materials during ambient storage and their in situ regeneration
CN104934608A (en) Preparation method of in-situ graphene coated lithium ion battery cathode material
CN102306783A (en) Multi-layer graphene/lithium iron phosphate intercalated composite material, preparation method thereof, and lithium ion battery adopting multi-layer grapheme/lithium iron phosphate intercalated composite material as anode material
CN103496741B (en) A kind of solid phase reaction method prepares Li 3vO 4negative material
CN101572327A (en) Lithium ion battery adopting graphene as cathode material
CN103872287A (en) Composite positive electrode material of graphene and lithium iron phosphate battery and preparation method thereof
CN103346317B (en) Composite mixed and cladded type anode material for lithium-ion batteries LiFePO 4and preparation method thereof
CN102169985A (en) Preparation method of lithium ion battery carbon anode material with graphene-like structure
CN101290986B (en) Preparing method of Li3V2(PO4)3/C positive pole and prepared positive pole material
CN104600309A (en) Preparation method of secondary start-up lithium ion battery cathode material
CN102751493A (en) Preparation method of lithium iron phosphate
CN103078089B (en) Composite graphite cathode material for high-capacity lithium ion battery, and its preparation method
CN108682804B (en) Preparation method of lithium ion battery cathode material with hard carbon-coated soft carbon
Mo et al. Engineering electrode/electrolyte interphase chemistry toward high-rate and long-life potassium ion full-cell
CN102110813A (en) Graphite material at negative pole of lithium ion battery and preparation method thereof
CN103972489A (en) Negative electrode material, preparation method thereof and lithium ion battery with same

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20180727

Address after: 405400 Chongqing Kai Zhou Industrial Park, Zhao Jia light industrial food industry park No. 5 standard workshop.

Patentee after: CHONGQING JIABAOCHENG ENERGY TECHNOLOGY CO., LTD.

Address before: 443002 No. 8, University Road, Yichang, Hubei

Patentee before: China Three Gorges University

TR01 Transfer of patent right
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20151111

Termination date: 20210311

CF01 Termination of patent right due to non-payment of annual fee