CN105390680B - A kind of preparation method of lithium ion battery negative material - Google Patents

A kind of preparation method of lithium ion battery negative material Download PDF

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CN105390680B
CN105390680B CN201510849597.1A CN201510849597A CN105390680B CN 105390680 B CN105390680 B CN 105390680B CN 201510849597 A CN201510849597 A CN 201510849597A CN 105390680 B CN105390680 B CN 105390680B
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lithium ion
ion battery
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CN105390680A (en
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韩生
刘金宝
蔺华林
冯晨萁
刘益林
艾亚妮
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Shanghai Institute of Technology
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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
    • 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
    • H01M4/13—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • 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

A kind of preparation method of lithium ion battery negative material of the present invention, by CNFs it is acidified it is processed after, centrifugation washing, it is distributed in water, scattered CNFs is mixed with scattered aniline and lauryl sodium sulfate aqueous solution, is ultrasonically formed the mixed liquor of stable and uniform, ice water stirs and the ammonium persulfate of acidification is added, obtained dispersion liquid obtains CNFs@PANI by centrifugation, washing, adds Na2MoO4And Na2S, stops heating, and natural cooling stirring obtains CNFs@PANI/MoS3, then calcining carbonization at high temperature, finally obtains CNFs@NC/MoS2.Molybdenum disulfide volume expansion caused by inherent level that the method for the present invention can effectively prevent to crush using the polyaniline of growth in situ, so that the stability of composite negative pole material is good, it is easy to control, and the electric conductivity of material can be effectively improved, substantially increase the specific capacity and high rate performance of battery.

Description

A kind of preparation method of lithium ion battery negative material
Technical field
The invention belongs to materialogy fields, are related to a kind of lithium ion battery, specifically a kind of negative electrode of lithium ion battery The preparation method of material.
Background technology
The lithium rechargeable battery being increasingly commercialized is limited to theoretical capacity, and it is close can not further to significantly improve its energy Degree, and fuel cell yet more difficult functionization in a short time, the technology grasped at present is far from meeting the needs of developing.And The new chemical energy that lithium ion battery rises as the 90's of 20th century, with energy density is big, self discharge is small, the cycle longevity The advantages that life is long, working range is wide, memory-less effect and environmental pollution are small has been widely used in mobile phone, notebook electricity In the portable electronic products such as brain, video camera, digital camera, in recent years, lithium ion battery be widely applied to again electric bicycle, The large capacities energy storage device such as aerospace field.So we are being dedicated to changing lithium ion battery negative material always Into to improve the chemical property of lithium ion battery negative material.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides a kind of preparations of lithium ion battery negative material The preparation method of method, this lithium ion battery negative material solves negative electrode of lithium ion battery material in the prior art The stability difference of the material technical problem low with high rate performance.
The present invention provides a kind of preparation methods of lithium ion battery negative material, include the following steps：
1) the step of carbon nano-fiber aqueous solution of a preparation acidification；
By CNFs and HNO31 ~ 3h is stirred at 60 ~ 90 DEG C, is washed 1 ~ 5 time and is distributed in water through centrifugation；The CNFs With HNO320 ~ 40mg of material ratio：5ml, HNO3Mass percent concentration be 10 ~ 30%；
2) method by in-situ polymerization prepares the step of carbon nano-fiber of polyphenyl amino-functionalization；
Aniline and lauryl sodium sulfate are added to the water dispersion together, the aniline and lauryl sodium sulfate Material ratio is 0.1 ~ 0.2ml：8 ~ 12mg, by scattered mixed solution and step（1）The carbon nano-fiber aqueous solution of middle acidification The material ratio of mixing, the aniline and carbon nano-fiber is 0.1 ~ 0.2ml:20 ~ 40 mg, ultrasound 10 ~ 50 minutes are formed steady Fixed mixed liquor, is then stirred in ice-water bath, and is added with the acidified ammonium persulfate of 0.8 ~ 1.2mol/L hydrochloric acid, described The material ratio of ammonium persulfate and hydrochloric acid is 0.5 ~ 1g:The material ratio of 50ml, the ammonium persulfate and carbon nano-fiber be 0.5 ~ 1g:20 ~ 40mg is stirred 10 ~ 20 hours, and obtained mixed liquor obtains CNFs PANI 1 ~ 5 time by centrifugation washing；
3) the step of carbonization；
In step（2）NaMoO is added in obtained CNFs@PANI41 ~ 5h is stirred at 60 ~ 90 DEG C, is added NaMoO4The material ratio for the carbon nano-fiber being added with front is 0.2 ~ 0.4g:Then Na is added in 0.02 ~ 0.04g thereto2S, NaMoO4And Na20.2 ~ 0.4g of S material ratios:0.4~1g.Stop heating, natural cooling obtains CNFs@PANI/MoS3, in inertia Under the atmosphere of gas, 700 ~ 900 DEG C of progress carbonization treatments are warming up to, CNFs@NC/MoS are finally obtained2。
Further, step（3）Described in inert gas atmosphere be nitrogen.
Further, step 2）In, in ultrasound and whipping process, maintain water temperature at 0 ~ 5 DEG C.
Further, step（3）In, first in 60 DEG C of isothermal reaction 5h, then 800 DEG C are warming up to, keep 2h.
By the CNFs of acidification, centrifugation washing is distributed in water the present invention, by scattered CNFs with it is scattered scattered Aniline and lauryl sodium sulfate（SDS）Aqueous solution mixes, and by being ultrasonically formed the mixed liquor of stable and uniform, ice water stirs simultaneously It is slowly added to the ammonium persulfate of acidification（APS）To overnight, obtained dispersion liquid obtains CNFs@PANI by centrifugation, washing, then adds Enter Na2MoO4And Na2S obtains CNFs@PANI/MoS3, then be carbonized and finally obtain CNFs@NC/MoS2。
The polyaniline-coated MoS for the carbonization that this preparation method is prepared2/ CNFs composite materials, fully by molybdenum disulfide Excellent electrochemical theoretical capacity and preferable security performance and the high conductivity of CNFs can apply to negative electrode of lithium ion battery material In material, but due to the stacked in layers structure of molybdenum disulfide, volume change is easy tod produce during lithium ion multiple intercalation/deintercalation Change, to influence its chemical property, so we prevent the volume in it in level by the method for polyaniline in-situ polymerization Expansion, to improve its electrochemical stability.
The present invention can effectively prevent the molybdenum disulfide crushed from being caused by inherent level using the polyaniline of growth in situ Volume expansion it is easy to control so that the stability of composite positive pole is good, and can effectively improve leading for material Electrically, the specific capacity and high rate performance for substantially increasing electrode, to obtain high performance lithium ion battery negative material.
The present invention is compared with prior art, and technological progress is significant.Present invention process process is simple, strong operability, Equipment investment is few, and production cost is low, the polyaniline-coated MoS of gained carbonization2The electrochemical stabilities of/CNFs composite materials is good, Specific capacity height, good cycle, high rate performance are excellent, are suitable for power battery application field.
Description of the drawings
A in Fig. 1, b are the SEM figures for the carbon nano-fiber being acidified in embodiment 1, and c, d are the CNFs@NC/ after carbonization treatment MoS2SEM figure
Fig. 2 is the CNFs@NC/MoS that embodiment 2 synthesizes2HTEM figure.
Fig. 3 is the CNFs@NC/MoS that embodiment 2 synthesizes2XRD（A）、CV（B）, circulation volume（C）And high rate performance（D） Figure.
Fig. 4 is the CNFs@NC/MoS that embodiment 2 synthesizes2Infrared figure.
Specific implementation mode
Technical solutions according to the invention are further described in detail below by specific embodiment, but it is necessary to It points out that following embodiment is served only for the description to invention content, does not constitute limiting the scope of the invention.
Embodiment 1
A kind of preparation method of lithium ion battery negative material, steps are as follows：
By 30mg CNFs and 5ml HNO32h is stirred at 80 DEG C, washing several times through centrifugation is distributed in 50ml water.It will 0.12ml aniline and 10mg SDS are added to ultrasonic disperse in 50ml water together, by scattered mixed solution and acidified carbon Nanofiber aqueous solution mixes, and continues ultrasound 15 minutes, forms stable mixed liquor, is stirred through ice-water bath, is slowly added to simultaneously 0.7g ammonium persulfates through 50ml 1M HCl acidifications, to overnight, obtained mixed liquor obtains three times by centrifugation washing for stirring CNFs@PANI.300mg NaMoO are added in obtained CNFs@PANI43h is stirred at 80 DEG C, and 750mg is added thereto Na2S closes heating, after natural cooling, obtains CNFs@PANI/MoS3。
Embodiment 2
The CNFs@PANI/MoS that will be obtained in embodiment 13In the tube furnace for being passed through nitrogen, temperature programming carbonization treatment, At 60 DEG C, isothermal reaction 5h, then temperature programming keeps 2h to 800 DEG C.Finally obtain CNFs@NC/MoS2。
As it can be seen that the polyaniline of growth in situ is deposited on MoS2On/CNFs composite materials, curing can be effectively prevented It is greatly improved because of synergistic effect so that the advantage of three kinds of materials is all fully played in the volume expansion of level in molybdenum The chemical property of lithium ion battery negative material, to which the polyaniline for obtaining high performance lithium ionic cell cathode material carbonization is poly- Close MoS2/ CNFs composite materials.

Claims (3)

1. a kind of preparation method of lithium ion battery negative material, it is characterised in that include the following steps：
1) the step of carbon nano-fiber aqueous solution of a preparation acidification；
By CNFs and HNO31 ~ 3h is stirred at 60 ~ 90 DEG C, is washed 1 ~ 5 time and is distributed in water through centrifugation；The CNFs and HNO3 20 ~ 40mg of material ratio：5ml, HNO3Mass percent concentration be 10 ~ 30%；
2) method by in-situ polymerization prepares the step of carbon nano-fiber of polyphenyl amino-functionalization；
Aniline and lauryl sodium sulfate are added to the water dispersion together, the material of the aniline and lauryl sodium sulfate Than being 0.1 ~ 0.2ml：8 ~ 12mg, by scattered mixed solution and step（1）The carbon nano-fiber aqueous solution of middle acidification mixes, The material ratio of the aniline and carbon nano-fiber is 0.1 ~ 0.2ml:20 ~ 40 mg, ultrasound 10 ~ 50 minutes form stable mix Liquid is closed, is then stirred in ice-water bath, and be added with the acidified ammonium persulfate of 0.8 ~ 1.2mol/L hydrochloric acid, the persulfuric acid The material ratio of ammonium and hydrochloric acid is 0.5 ~ 1g:The material ratio of 50ml, the ammonium persulfate and carbon nano-fiber is 0.5 ~ 1g:20~ 40mg is stirred 10 ~ 20 hours, and obtained mixed liquor obtains CNFs PANI 1 ~ 5 time by centrifugation washing；
3) the step of carbonization；
In step（2）NaMoO is added in obtained CNFs@PANI41 ~ 5h, the NaMoO being added are stirred at 60 ~ 90 DEG C4With The material ratio for the carbon nano-fiber that front is added is 0.2 ~ 0.4g:Then Na is added in 0.02 ~ 0.04g thereto2S, NaMoO4With Na20.2 ~ 0.4g of S material ratios:0.4 ~ 1g, stops heating, and natural cooling obtains CNFs@PANI/MoS3, in the gas of inert gas Under atmosphere, 700 ~ 900 DEG C of progress carbonization treatments are warming up to, CNFs@NC/MoS are finally obtained2。
2. a kind of preparation method of lithium ion battery negative material according to claim 1, it is characterised in that：Step 2） In, in ultrasound and whipping process, maintain water temperature at 0 ~ 5 DEG C.
3. a kind of preparation method of lithium ion battery negative material according to claim 1, it is characterised in that：Step（3） In, first in 60 DEG C of isothermal reaction 5h, then 800 DEG C are warming up to, keep 2h.
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CN105924665B (en) * 2016-04-26 2018-10-30 上海应用技术学院 A kind of preparation method and applications of superhigh cross-linking layering microporous polymer
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Citations (1)

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CN104269537A (en) * 2014-09-28 2015-01-07 南京中储新能源有限公司 Nano polyaniline sulfenyl composite material and application of nano polyaniline sulfenyl composite material

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KR101558535B1 (en) * 2008-12-02 2015-10-07 삼성전자주식회사 Negative active material negative electrode comrprising same method of preparing negative electrodee and lithium battery

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CN104269537A (en) * 2014-09-28 2015-01-07 南京中储新能源有限公司 Nano polyaniline sulfenyl composite material and application of nano polyaniline sulfenyl composite material

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* Cited by examiner, † Cited by third party
Title
Polypyrrole-assisted synthesis of roselike MoS2/nitrogen-containing carbon/graphene hybrids and their robust lithium storage performances;Zhiyan Guo等;《RSC Advances》;20150708;第5卷;第62624-62629页 *

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