CN107706369A - A kind of preparation method of CNT and LiFePO 4 composite positive pole - Google Patents

A kind of preparation method of CNT and LiFePO 4 composite positive pole Download PDF

Info

Publication number
CN107706369A
CN107706369A CN201710808117.6A CN201710808117A CN107706369A CN 107706369 A CN107706369 A CN 107706369A CN 201710808117 A CN201710808117 A CN 201710808117A CN 107706369 A CN107706369 A CN 107706369A
Authority
CN
China
Prior art keywords
lifepo
cnt
preparation
composite positive
positive pole
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.)
Pending
Application number
CN201710808117.6A
Other languages
Chinese (zh)
Inventor
朱德康
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.)
Mianyang Ping Ping Technology Co Ltd
Original Assignee
Mianyang Ping Ping Technology Co Ltd
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 Mianyang Ping Ping Technology Co Ltd filed Critical Mianyang Ping Ping Technology Co Ltd
Priority to CN201710808117.6A priority Critical patent/CN107706369A/en
Publication of CN107706369A publication Critical patent/CN107706369A/en
Pending legal-status Critical Current

Links

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
    • 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
    • H01M4/58—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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Catalysts (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides the preparation method of a kind of CNT and LiFePO 4 composite positive pole, belongs to energy and material preparation field.Preparation method is to mix Fe, Ni catalyst, talcum powder with LiFePO 4 particle, catalytic pyrolysis carbon source under high temperature, grows CNT in particle surface, prepares LiFePO4/ CNT composite positive poles.Present invention improves the electronics of LiFePO 4 and ionic conductivity be relatively low, high-power discharge and recharge when performance be remarkably decreased the shortcomings that；Present invention process is simple, product is compound uniformly, provides a kind of novel anode material for lithium battery, has certain application prospect.

Description

A kind of preparation method of CNT and LiFePO 4 composite positive pole
Technical field
The present invention is to be received on lithium ion battery, more particularly to a kind of LiFePO 4 for preparing lithium ion battery with carbon Mitron (LiFePO4/ CNT) composite positive pole method.
Background technology
It is excellent that lithium ion battery has high-energy-density, good cycle performance, memory-less effect, operating temperature range wide etc. Point, there is very big application prospect in the large-sized power field of power supplies such as electric car.The LiFePO 4 of olivine structural (LiFePO4) positive electrode has abundant raw material sources, cheap, non-environmental-pollution, the higher (theoretical capacity of capacity 170mAh/g) the advantages that, is as the focus applied at present.
LiFePO 4 exist electronics and ionic conductivity is relatively low, high-power discharge and recharge when performance the shortcomings that being remarkably decreased. The method on improving LiFePO 4 performance mainly has carbon coating and metal ion mixing etc. at present.
CNT is a kind of new carbon structure found the 1990s, and it is a kind of hollow tubular structure, pipe Wall forms for one or more layers graphene curling.This structure of CNT has excellent electronics, machinery, optics, heat And energy-storage property, so as to obtain extensive concern.In recent years, people are carried out compound with lifting using CNT and energy and material The chemical property of material, such as lithium ion battery, solar cell.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of LiFePO4/CNT positive electrodes, NEW TYPE OF COMPOSITE material is prepared Material, improve the performance of LiFePO 4, overcome electronics existing for LiFePO 4 and ionic conductivity is relatively low, high-power charge and discharge The shortcomings that performance is remarkably decreased when electric.
A kind of CNT of the present invention and the preparation method of LiFePO 4 composite positive pole, have following steps：
The preparation method of a kind of CNT and LiFePO 4 composite positive pole, has following steps：
(1) in mass ratio 1: 10: 100 catalyst, talcum powder and ferrous phosphate lithium powder are weighed, is added to absolute ethyl alcohol or distillation In water, 10~60min of grinding stirring or ultrasonic mixing, the LiFePO 4 that supported catalyst is made in 60~80 DEG C of drying carries Body；
The catalyst is the one or several kinds in ferric nitrate, ferrocene, nickelous carbonate, nickel hydroxide, nickel acetate.
(2) LiFePO 4 carrier made from step (1) being laid on alumina substrate, substrate is placed on quartz boat, Quartz boat is placed on the quartz ampoule pipe head end portion of tube furnace.It is passed through 10~30min of inert gas and excludes inner air tube.
The inert gas is one kind in argon gas, nitrogen or both mixing.
(3) tube furnace being warming up to 600~850 DEG C of catalytic reaction temperature, push-in quartz boat is central to stove, insulation 5~ 10min, reducing gas is passed through, phase carbon source is injected from tube furnace inlet end with syringe, noted with 10~15ml/h speed Enter 20~40 min, under reducing atmosphere, stop heating and cool to normal temperature with the furnace, take out sample in tube furnace, obtain phosphoric acid Asia Iron lithium and carbon nano tube compound material.
The phase carbon source is ethanol, methanol, hexamethylene, benzene, one kind in toluene or mixing.
The reducing gas is that hydrogen mixes with one or any in argon gas, nitrogen.
The preferred mass ratio of step (1) catalyst and ferrous phosphate lithium powder is 1: 40.
The preferable temperature of step (3) catalytic reaction is 750 DEG C.
It is 12ml/h that step (3) carbon source, which is preferably injected speed, and it is 30min to be preferably injected the time.
The invention has the advantages that provide a kind of LiFePO4The preparation method of/CNT positive electrodes.The preparation method Can be uniformly compound with CNT by LiFePO 4 particle, the electronics and the ionic conductivity that improve LiFePO 4 be relatively low, The shortcomings that performance is remarkably decreased during high-power discharge and recharge.Present invention process is simple, product is compound uniformly, and one kind is provided for lithium battery Novel anode material, there is certain application prospect.
Embodiment
The present invention uses commercially available chemical pure raw material, and the present invention is given furtherly by the following specific embodiments It is bright.
Embodiment 1
In mass ratio 1: 10: 100 weighs nickelous carbonate, talcum powder and ferrous phosphate lithium powder, is added in absolute ethyl alcohol, grinding 30min.80 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 150sccm speed.
Tube furnace is warming up to 750 DEG C, push-in quartz boat to stove center, after 5min, Ar gas air-flows are adjusted to 300sccm, and 15 Ml/h injects hexamethylene, fluid injection 40min.Stop heating, cool to normal temperature with the furnace under argon gas protection, take out sample in tube furnace Product, as LiFePO4/CNT composites.
Embodiment 2：
Ferrocene, talcum powder and ferrous phosphate lithium powder are weighed by 1: 10: 100, is added in absolute ethyl alcohol, grinding stirring 30min.60 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 500sccm speed.
Tube furnace is warming up to 850 DEG C, push-in quartz boat to stove center, after 5min, Ar gas air-flows are adjusted to 300sccm, and 15 Ml/h injection ethanol 30min.Stop heating, cool to normal temperature with the furnace under argon gas protection, take out sample in tube furnace, be LiFePO4/CNT composites.
Embodiment 3：
Ferric nitrate and nickel hydroxide, talcum powder and ferrous phosphate lithium powder are weighed by 1: 10: 100, is added in distilled water, is ground Stir 30min.60 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 500sccm speed.
Tube furnace is warming up to 750 DEG C, push-in quartz boat to stove center, after 5min, Ar gas air-flows are adjusted to 300sccm, and 15 Ml/h injection ethanol 40min.Stopping heating, cooling to normal temperature with the furnace under argon gas protection, take out sample in tube furnace, i.e., For LiFePO4/CNT composites.
Embodiment 4：
In mass ratio 1: 10: 100 weighs nickel acetate, talcum powder and ferrous phosphate lithium powder, is added in absolute ethyl alcohol, and ultrasound is mixed Close 30min.60 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 300sccm speed.
Tube furnace is warming up to 700 DEG C, push-in quartz boat to stove center, after 5min, Ar gas air-flows are adjusted to 150sccm, and 10 Ml/h injects benzene and the mixed liquor 30min of toluene 1: 1.Stop heating, cool to normal temperature with the furnace under nitrogen protection, take out tubular type Sample in stove, as LiFePO4/CNT composites.
Embodiment 5：
In mass ratio 1: 10: 100 weighs ferric nitrate, talcum powder and ferrous phosphate lithium powder, is added in absolute ethyl alcohol, grinding is stirred Mix 30min.60 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 500sccm speed.
Tube furnace is warming up to 800 DEG C, push-in quartz boat is central to stove, and after 5min, Ar gas air-flows are adjusted to 300sccm, leads to Enter H2100sccm, 15ml/h injection 5ml methanol and 6ml ethanol mixed liquor 30min.Stop heating, argon gas protection under with Stove is cooled to normal temperature, takes out sample, as LiFePO4/CNT composites in tube furnace.
Embodiment 6：
In mass ratio 1: 10: 100 weighs nickelous carbonate, talcum powder and ferrous phosphate lithium powder, is added in absolute ethyl alcohol, and ultrasound is mixed Close 30min.60 DEG C of drying, the LiFePO 4 carrier of supported catalyst is made.
LiFePO 4 carrier is laid on alumina substrate, substrate is placed on quartz boat, and quartz boat is placed on tube furnace Quartz ampoule pipe head end portion.Ar gas is passed through half an hour exclusion inner air tube with 150sccm speed.
Tube furnace is warming up to 600 DEG C, push-in quartz boat to stove center, after 5min, Ar gas air-flows are adjusted to 300sccm, and 12 Ml/h injection hexamethylenes 40min.Stop heating, cool to normal temperature with the furnace under inert atmosphere protection, take out sample in tube furnace Product, as LiFePO4/CNT composites.
LiFePO4/CNT composites prepared by the present invention, detection method are to sample by SEM Carry out morphology analysis, and the electrical conductivity of test material.

Claims (4)

1. the preparation method of a kind of CNT and LiFePO 4 composite positive pole, has following steps：
(1) in mass ratio 1: 10: 100 catalyst, talcum powder and ferrous phosphate lithium powder are weighed, is added to absolute ethyl alcohol or distillation In water, 10~60min of grinding stirring or ultrasonic mixing, the LiFePO 4 that supported catalyst is made in 60~80 DEG C of drying carries Body；
The catalyst is the one or several kinds in ferric nitrate, ferrocene, nickelous carbonate, nickel hydroxide, nickel acetate；
(2) LiFePO 4 carrier made from step (1) is laid on alumina substrate, substrate is placed on quartz boat, quartz Boat is placed on the quartz ampoule pipe head end portion of tube furnace；It is passed through 10~30min of inert gas and excludes inner air tube；
The inert gas is one kind in argon gas, nitrogen or both mixing；
(3) tube furnace is warming up to 600~850 DEG C of catalytic reaction temperature, push-in quartz boat to stove center, is incubated 5~10min, Be passed through reducing gas, injected phase carbon source from tube furnace inlet end with syringe, with 10~15ml/h speed injection 20~ 40min；Stop heating, cool to normal temperature with the furnace under inert atmosphere protection, take out sample in tube furnace, obtain ferrous phosphate Lithium and carbon nano tube compound material；
The reducing gas is that hydrogen mixes with one or any in argon gas, nitrogen；
The phase carbon source is the one or any mixing in ethanol, methanol, hexamethylene, benzene, toluene.
2. the preparation method of CNT according to claim 1 and LiFePO 4 composite positive pole, it is characterised in that The preferred mass ratio of step (1) catalyst and ferrous phosphate lithium powder is 1: 40.
3. the preparation method of CNT according to claim 1 and LiFePO 4 composite positive pole, it is characterised in that The preferable temperature of step (3) catalytic reaction is 750 DEG C.
4. the preparation method of CNT according to claim 1 and LiFePO 4 composite positive pole, it is characterised in that It is 12ml/h that step (3) carbon source, which is preferably injected speed, and it is 30min to be preferably injected the time.
CN201710808117.6A 2017-09-08 2017-09-08 A kind of preparation method of CNT and LiFePO 4 composite positive pole Pending CN107706369A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710808117.6A CN107706369A (en) 2017-09-08 2017-09-08 A kind of preparation method of CNT and LiFePO 4 composite positive pole

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710808117.6A CN107706369A (en) 2017-09-08 2017-09-08 A kind of preparation method of CNT and LiFePO 4 composite positive pole

Publications (1)

Publication Number Publication Date
CN107706369A true CN107706369A (en) 2018-02-16

Family

ID=61172316

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710808117.6A Pending CN107706369A (en) 2017-09-08 2017-09-08 A kind of preparation method of CNT and LiFePO 4 composite positive pole

Country Status (1)

Country Link
CN (1) CN107706369A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544499A (en) * 2012-03-14 2012-07-04 天津大学 Method for preparing lithium ferrous phosphate (LiFePO4) and carbon nano tube composite cathode material for lithium battery
CN106887570A (en) * 2017-03-01 2017-06-23 沧州锐星化学科技有限公司 Lithium-ion-power cell LiFePO 4 composite positive pole and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102544499A (en) * 2012-03-14 2012-07-04 天津大学 Method for preparing lithium ferrous phosphate (LiFePO4) and carbon nano tube composite cathode material for lithium battery
CN106887570A (en) * 2017-03-01 2017-06-23 沧州锐星化学科技有限公司 Lithium-ion-power cell LiFePO 4 composite positive pole and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
朱洪法: "《生活化学品与健康》", 1 April 2013 *

Similar Documents

Publication Publication Date Title
CN107093732B (en) A kind of lithium iron phosphate/carbon nano-tube nano composite material and preparation method for anode material of lithium battery
CN105489864B (en) A kind of Asia titanium-oxide-coated modified phosphate iron lithium composite material and preparation method thereof
CN103427073B (en) A kind of preparation method of the mesoporous Si/C complex microsphere as lithium cell cathode material
CN102544499A (en) Method for preparing lithium ferrous phosphate (LiFePO4) and carbon nano tube composite cathode material for lithium battery
CN106129337B (en) A kind of preparation method of cathode of lithium iron phosphate lithium ion battery electrode
CN102361073B (en) Preparation method of lithium ion battery silicon aluminium carbon composite cathode material
CN101442126B (en) Carbon nanotube key joint lithium iron phosphate composite electrode material and preparation method thereof
CN104124452B (en) A kind of coated lithium iron phosphate positive material of titanium compound and preparation method thereof that conducts electricity
CN105470468A (en) Fluorine-doped lithium ferric manganese phosphate cathode material and preparation method thereof
CN103219499B (en) A kind of preparation method of lithium ion battery silicon oxide/carbon composite negative pole material
CN103545492B (en) The preparation method of the multiple composite anode material of lithium ion battery
CN103159201B (en) A kind of high pressure, low temperature method preparing carbon-coated LiFePO 4 for lithium ion batteries anode composite material of lithium ion battery
Wang et al. Hydrothermal for synthesis of CoO nanoparticles/graphene composite as Li-ion battery anodes
Yu et al. Design and facile synthesis of nitrogen-doped carbon decorated LiVPO4F nanocrystals as superior cathode for lithium-ion batteries
CN101850957A (en) Method for preparing nano-lithium iron phosphate of cathode material of lithium ion battery
CN112289985B (en) C @ MgAl2O4Composite coating modified silicon-based negative electrode material and preparation method thereof
CN111900366B (en) SiO containing lithium x Method for preparing powder
CN102593462A (en) Method for preparing lithium iron phosphate by coating carbon
CN107845792A (en) A kind of LiFePO4 with loose structure/graphene composite lithium ion battery positive electrode
CN107706369A (en) A kind of preparation method of CNT and LiFePO 4 composite positive pole
CN106328951A (en) Preparation method of porous carbon electrode material of lithium-sulfur battery
CN106099060A (en) Method of electrostatic spinning prepares the lithium mesoporous lithium iron phosphate/carbon micro belt positive electrode of electricity
CN103000895B (en) A kind of preparation method of lithium battery nano-carbon coated lithium iron phosphate cathode material
CN111129495B (en) Preparation method of graphene battery negative electrode material
CN109860527B (en) Carbon-based composite material for preparing lithium battery cathode and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20180216