CN105680024A - Preparing method for lithium ion battery negative material FeS/CPAN - Google Patents

Preparing method for lithium ion battery negative material FeS/CPAN Download PDF

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Publication number
CN105680024A
CN105680024A CN201610226558.0A CN201610226558A CN105680024A CN 105680024 A CN105680024 A CN 105680024A CN 201610226558 A CN201610226558 A CN 201610226558A CN 105680024 A CN105680024 A CN 105680024A
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fes
cpan
lithium ion
ion battery
negative material
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CN201610226558.0A
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CN105680024B (en
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郭胜平
李加闯
薛怀国
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Yangzhou University
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Yangzhou University
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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
    • H01M4/36—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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a preparing method for a lithium ion battery negative material FeS/CPAN (carbonized polyacrylonitrile), and belongs to the field of energy storage.The preparing method includes the steps that Fe, S and PAN are mixed, ground uniformly and tableted, the obtained tablet is sealed in a quartz tube in a vacuum mode, the quartz tube is put into a muffle furnace to be subjected to a heating reaction, and a target product FeS/CPAN is obtained.It is proved through powder X-ray diffraction that the product is pure-phase FeS/CPAN; it is shown through scanning electron microscope representation that the prepared FeS particles are uniformly dispersed in holes in the surface of a CPAN substrate, the structure is beneficial for restraining volume expansion of FeS in the charging and discharging process, the circulation stability is improved, and the lithium ion battery negative material has great potential.The preparing method has simple operation steps, is short in preparation cycle and provides a new thought for preparing a FeS/C, or FeS2/C or FeSe/C composite electrode material in situ.

Description

The preparation method of lithium ion battery negative material FeS/CPAN
Technical field
The invention belongs to energy storage field, particularly a kind of lithium ion battery negative material FeS/CPAN(silicon carbide/polypropylene nitrile) preparation method.
Background technology
Along with the fast development of lithium ion battery, people are also more and more urgent for the demand of lithium ion battery with high energy density. For lithium ion battery, it is resolved that the mainly positive electrode material of its amount of capacity and negative material. At present, the negative material of the marketization is graphite. Although Graphite Electrodes has stable cycle performance, but its capacity too low (theoretical capacity is only 372mAh/g), can not meet people to the demand of high capacity lithium ion battery. Therefore, find a kind of cheapness, focus that negative material that high-energy-density, cycle performance are good has become research field of lithium ion battery. Fe and S also exists widely at nature, cheap, and environmentally friendly, is desirable lithium ion battery negative material. In addition, FeS has higher capacity (609mAh/g), good high rate performance, it is possible to meet people to the demand of lithium ion battery with high energy density. But, the cycle performance of FeS is poor, and after several circulations, loading capacity decays to about 300mAh/g. In order to improve the cyclical stability of FeS, investigator has done a large amount of explorations. Such as, the size of control FeS, at nano level, adopts Graphene and FeS compound etc. Above method of modifying all makes the cycle performance of FeS be significantly improved.
In the preparation method of FeS electrode materials, document often adopts hydrothermal method to prepare, and the presoma of conventional FeS presoma and multi-form carbon material or carbon material carrys out compound. Although these methods can obviously improve the cycle performance of FeS, but step is many, the combination of complicated operation and FeS and C is not tight.
Summary of the invention
It is an object of the invention to propose that a kind of method is simple, quick, equipment requirements is close to the preparation method of the lithium ion battery negative material FeS/CPAN of industrial applications demand.
The present invention comprises the following steps:
1) by Fe, S and PAN(polyacrylonitrile) after mixing grinding evenly, compressing tablet, obtains sheet work piece;
2) being vacuum-sealed in silica tube by sheet work piece, then silica tube is placed in retort furnace reacting by heating, reaction drops to room temperature after terminating, and obtains lithium ion battery negative material FeS/CPAN.
Raw material of the present invention needs grinding evenly after mixing, to guarantee that three kinds of reaction raw materials fully mix. After grinding evenly, sample is pressed into sheet so that the contact of Fe, S and PAN is finer and close, promotes that solid state reaction is more thorough. The present invention adopts one pot of original position solid phase method to prepare lithium ion battery negative material FeS/CPAN, and wherein FeS particle is relatively dispersed in the hole of CPAN matrix surface, soilless sticking phenomenon. The FeS that the inventive method generates can be dispersed on carbon base body, inhibits the volumetric expansion of FeS in charge and discharge process, thus improves the cycle performance of FeS. The inventive method is simple, fast, closer to the demand of industrial applications in the requirement of equipment.
In order to make full use of raw material, forming FeS compound, the mixing mol ratio of Fe and S of the present invention is 1: 1.
The total mass of described Fe and S is 3: 2 with the mixing quality ratio of PAN. This proportioning is conducive to the FeS generated to be evenly distributed on the carbon base body after PAN carbonization.
Silica tube is placed in retort furnace, reacts 12 hours after being heated to 600 DEG C with the temperature rise rate of 40～60 DEG C/h, then dropped to room temperature with 24 hours. Consider that raw material sublimed sulphur at high temperature easily distils and cause blasted pipe phenomenon, cause a large amount of losses reacted failure or cause element sulphur. And temperature of reaction to be defined as 600 DEG C be because carbonization occurs PAN in this temperature range, the effect that can play restriction lithium sulfide product containing N carbocyclic ring obtained, improves further cyclical stability and electric conductivity.
Oxyhydrogen flame and vacuum system is adopted to be vacuum-sealed in silica tube by sheet work piece; it is to guarantee that reaction carries out under the high vacuum environment of anhydrous and oxygen-free; relative inertness atmosphere protection is more effective, more can avoid S effusion at high temperature, thus obtain target product.
Accompanying drawing explanation
Fig. 1 is the XRD comparison diagram of embodiment of the present invention product FeS/CPAN and standard FeS.
Fig. 2 is the SEM figure of the FeS/CPAN adopting the inventive method to prepare.
Fig. 3 is the element map figure of C, N, Fe and the S in the FeS/CPAN for preparing of the inventive method.
Fig. 4 and Fig. 5 is respectively the charge-discharge test data that FeS/CPAN is used as lithium ion battery negative material.
Embodiment
In order to make the object of the present invention, technical scheme and advantage clearly understand, below in conjunction with embodiment, the present invention is described in detail.
One, preparation technology:
Taking Fe, S that total mass is 500mg, wherein the mol ratio of Fe and S is 1: 1.
Take 240mgPAN, fully it is ground to relatively fine powder.
Measured Fe and S of title is added in ground PAN powder, is ground to after mixing, it may also be useful to tabletting machine is by reaction raw materials compressing tablet. Oxyhydrogen flame and vacuum system is adopted to carry out vacuum sealing tube process subsequently.
The sample sealing pipe is put into retort furnace, sets heat treatment process and run: with the temperature rise rate of 40～60 DEG C/h, temperature in retort furnace is heated to 600 DEG C from room temperature, after reacting 12 hours under 600 DEG C of conditions, then drop to room temperature with 24 hours. Open silica tube and take out product, ground for subsequent use.
Two, product property:
Fig. 1 is the XRD figure of embodiment solid state reaction product FeS/CPAN. As seen from Figure 1: the XRD figure being obtained by reacting FeS/CPAN is consistent with the theoretical XRD figure of FeS.
Fig. 2 is the SEM figure adopting the FeS/CPAN of solid state reaction product in the corresponding embodiment of the inventive method. In high temperature sintering FeS/CPAN matrix material out, FeS particle is relatively dispersed in the hole of CPAN matrix surface.
Fig. 3 is element map figure. Even by each Elemental redistribution in the known FeS/CPAN of analysis of different elemental map, with sem analysis result is consistent above.
Fig. 4 and Fig. 5 is the electrochemical data of FeS/CPAN when being used as lithium ion battery negative material. Can find out, FeS/CPAN prepared by the inventive method, when it is used as lithium ion battery negative material, the initial specific discharge capacity up to 1426mAh/g (charging/discharging voltage scope is between 0.01 3.0V) is had, and initial charge specific storage reaches 1100mAh/g under 0.1C (60.9Am/g) electric current. This battery second time, for the third time specific discharge capacity, respectively up to 959mAh/g and 956mAh/g, have good coulombic efficiency. After 50,80 circulations, loading capacity also has 730 and 665mAh/g.
The above; it it is only the better embodiment of the present invention; not the present invention is done any restriction in form; any those skilled in the art; do not departing within the scope of technical solution of the present invention; according to the technical spirit of the present invention, any simple amendment above embodiment done, equivalent replacement and improvement etc., all still belong within the protection domain of technical solution of the present invention.

Claims (5)

1. the preparation method of lithium ion battery negative material FeS/CPAN, it is characterised in that comprise the following steps:
1) after Fe, S and PAN being mixed, grinding is evenly, and compressing tablet obtains sheet work piece;
2) being vacuum-sealed in silica tube by sheet work piece, then silica tube is placed in retort furnace reacting by heating, reaction drops to room temperature after terminating, and obtains lithium ion battery negative material FeS/CPAN.
2. the preparation method of lithium ion battery negative material FeS/CPAN according to claim 1, it is characterised in that: the mixing mol ratio of Fe and S is 1: 1.
3. the preparation method of lithium ion battery negative material FeS/CPAN according to claim 1 and 2, it is characterised in that: the total mass of described Fe and S is 3: 2 with the mixing quality ratio of PAN.
4. the preparation method of lithium ion battery negative material FeS/CPAN according to claim 1, it is characterized in that: silica tube is placed in retort furnace, react 12 hours after being heated to 600 DEG C with the temperature rise rate of 40～60 DEG C/h, then dropped to room temperature with 24 hours.
5. the preparation method of lithium ion battery negative material FeS/CPAN according to claim 1, it is characterised in that: adopt oxyhydrogen flame and vacuum system to be vacuum-sealed in silica tube by sheet work piece.
CN201610226558.0A 2016-04-13 2016-04-13 Lithium ion battery negative material FeS/CPAN preparation method Active CN105680024B (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229481A (en) * 2016-08-23 2016-12-14 扬州大学 The preparation method of transient metal sulfide/silicon carbide/polypropylene nitrile composite
CN109817915A (en) * 2019-01-18 2019-05-28 郑州中科新兴产业技术研究院 A kind of nanometer of iron compound/carbonaceous mesophase spherules composite material and preparation method
CN110364720A (en) * 2019-07-26 2019-10-22 南京海泰纳米材料有限公司 Positive electrode active materials and preparation method thereof, anode pole piece and preparation method based on positive electrode active materials preparation
CN110635125A (en) * 2019-10-12 2019-12-31 天目湖先进储能技术研究院有限公司 Preparation method of ferrous sulfide/carbon composite positive electrode material
CN111477857A (en) * 2020-04-28 2020-07-31 浙江理工大学 Hollow core-shell structure FeS2Preparation method and application of @ C nanocomposite
CN112700968A (en) * 2020-12-16 2021-04-23 安徽工业大学 Preparation method of iron sulfide-carbon composite electrode material, obtained electrode and application thereof
CN113517443A (en) * 2021-06-19 2021-10-19 天目湖先进储能技术研究院有限公司 Preparation method of polyacrylonitrile/iron disulfide composite positive electrode material for lithium secondary battery

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Publication number Priority date Publication date Assignee Title
CN1240765A (en) * 1999-07-15 2000-01-12 北京矿冶研究总院 Synthesis method of high-purity nickel disulfide powder
CN104362295A (en) * 2014-11-13 2015-02-18 四川浩普瑞新能源材料有限公司 Nickel-based anode material for lithium ion battery and preparation method of nickel-based anode material
CN104659384A (en) * 2013-11-18 2015-05-27 中国电子科技集团公司第十八研究所 Preparation method of large-capacity power-type lithium-ferrous disulfide (Li-FeS2) battery pack

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1240765A (en) * 1999-07-15 2000-01-12 北京矿冶研究总院 Synthesis method of high-purity nickel disulfide powder
CN104659384A (en) * 2013-11-18 2015-05-27 中国电子科技集团公司第十八研究所 Preparation method of large-capacity power-type lithium-ferrous disulfide (Li-FeS2) battery pack
CN104362295A (en) * 2014-11-13 2015-02-18 四川浩普瑞新能源材料有限公司 Nickel-based anode material for lithium ion battery and preparation method of nickel-based anode material

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106229481A (en) * 2016-08-23 2016-12-14 扬州大学 The preparation method of transient metal sulfide/silicon carbide/polypropylene nitrile composite
CN109817915A (en) * 2019-01-18 2019-05-28 郑州中科新兴产业技术研究院 A kind of nanometer of iron compound/carbonaceous mesophase spherules composite material and preparation method
CN110364720A (en) * 2019-07-26 2019-10-22 南京海泰纳米材料有限公司 Positive electrode active materials and preparation method thereof, anode pole piece and preparation method based on positive electrode active materials preparation
CN110364720B (en) * 2019-07-26 2021-02-05 南京海泰纳米材料有限公司 Positive active material, positive pole piece and preparation method thereof
CN110635125A (en) * 2019-10-12 2019-12-31 天目湖先进储能技术研究院有限公司 Preparation method of ferrous sulfide/carbon composite positive electrode material
CN111477857A (en) * 2020-04-28 2020-07-31 浙江理工大学 Hollow core-shell structure FeS2Preparation method and application of @ C nanocomposite
CN112700968A (en) * 2020-12-16 2021-04-23 安徽工业大学 Preparation method of iron sulfide-carbon composite electrode material, obtained electrode and application thereof
CN113517443A (en) * 2021-06-19 2021-10-19 天目湖先进储能技术研究院有限公司 Preparation method of polyacrylonitrile/iron disulfide composite positive electrode material for lithium secondary battery
CN113517443B (en) * 2021-06-19 2023-03-28 天目湖先进储能技术研究院有限公司 Preparation method of polyacrylonitrile/iron disulfide composite positive electrode material for lithium secondary battery

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