CN104393296A - Lithium ion battery composite positive electrode material and preparation method thereof - Google Patents

Lithium ion battery composite positive electrode material and preparation method thereof Download PDF

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Publication number
CN104393296A
CN104393296A CN201410736386.2A CN201410736386A CN104393296A CN 104393296 A CN104393296 A CN 104393296A CN 201410736386 A CN201410736386 A CN 201410736386A CN 104393296 A CN104393296 A CN 104393296A
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lithium
ion battery
lithium ion
battery composite
positive electrode
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CN104393296B (en
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伍凌
石少楠
钟胜奎
王鹏飞
苟生莲
丁浩
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Suzhou University
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Suzhou 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
    • H01M4/58—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
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a lithium ion battery composite positive electrode material with a structural formula of xLiCoPO4.yLi3V2(PO4)3, wherein x:y=(50:1) to (1:10). The composite positive electrode material is high in working voltage and specific capacity, is good in rate capability, is long in cyclic service life, is good in safety performance, is a novel high-energy-density lithium ion battery composite positive electrode material, and has a wide application prospect. The preparation method comprises the following steps of mixing precursor compounds containing cobalt and vanadium or crystalline hydrate of the precursor compounds with a lithium source and a phosphorus source uniformly, and sintering under the inert or reducing atmosphere at 550-850 DEG C for 4-24 hours, thereby obtaining the composite positive electrode material. The preparation method is relatively uniform in mixing, is beneficial to the development of the synergistic effect of LiCoPO4 and Li3V2(PO4)3 of the synthesized composite positive electrode material, so that the performances of the composite positive electrode material are relatively excellent.

Description

A kind of lithium ion battery composite cathode material and preparation method thereof
Technical field
The invention belongs to field of lithium ion battery, relate to a kind of anode material for lithium-ion batteries and preparation method thereof, be specifically related to a kind of lithium ion battery composite cathode material and preparation method thereof.
Background technology
In recent years, the compound L iMPO of olivine structural 4(M=Fe, Mn, Ni and Co etc.) theoretical capacity is high owing to having, good reversibility, thermal stability and the advantage such as fail safe is good, becomes the study hotspot of field of lithium ion battery anode.In these compounds, LiCoPO 4be considered to one very promising 5V level high-voltage anode material, because it has high specific energy density (~ 800Whkg -1), high operating voltage (~ 4.8V vs.Li/Li +), high theoretical specific capacity (167mAhg -1).But, LiCoPO 4there is very low electronic conductivity and lithium ion diffusion rate, make its chemical property poor.
Current to LiCoPO 4the emphasis of study on the modification concentrates on and improves its electronic conductivity and lithium ion diffusion rate two aspects, main path has Surface coating electronic conductor (as conductive carbon, conducting metal), gas ions phase-doped modified (magnesium ion, manganese ion, nickel ion, iron ion, vanadium ion, ruthenium ion etc.), or micronized particles.Although these methods make LiCoPO 4chemical property make moderate progress, but also need more effective method of modifying to commercialization.
Li 3v 2(PO 4) 3the another important member in phosphate system positive electrode.Because it has the features such as security performance is good, with low cost, Stability Analysis of Structures, chemical property are better, cause the extensive concern of researcher in recent years.Li 3v 2(PO 4) 3the high (~ 197mAhg of theoretical specific capacity -1), and lithium ion diffusion rate is large, good rate capability, because it has special three-dimensional ion channel, lithium ion can embed soon and deviate from crystal.Although Li 3v 2(PO 4) 3have better high rate performance and higher theoretical specific capacity, but its average working voltage is relatively low, it has three working voltage platform (~ 3.55V, 3.6V and 4.0V), and average working voltage is only ~ 3.8V (vs.Li/Li +), which limits its energy density.
Summary of the invention
In view of this, an object of the present invention is that providing a kind of improves LiCoPO 4li can be improved while conductivity and capacity 3v 2(PO 4) 3the lithium ion battery composite cathode material of operating voltage, energy density.
Concrete, the invention provides following technical scheme:
Lithium ion battery composite cathode material of the present invention, structural formula is xLiCoPO 4yLi 3v 2(PO 4) 3, described x and y meets x:y=50:1 ~ 1:10.
Preferably, described x and y meets x:y=20:1 ~ 1:2.
Further, electric conducting material is added with in described lithium ion battery composite cathode material.
Preferably, described electric conducting material is conductive carbon.
Use Li 3v 2(PO 4) 3fast ion conduction and high power capacity to LiCoPO 4material carries out modification, improves LiCoPO 4conductivity, specific capacity and high rate performance; Use LiCoPO 4high voltage to Li 3v 2(PO 4) 3modification, improves Li 3v 2(PO 4) 3energy density.Namely the Li with NASCION structure is utilized 3v 2(PO 4) 3be the advantage of fast lithium ion conductor (lithium ion transport speed is fast), improve LiCoPO 4ionic conductivity; And compared with the fast-ionic conductor of non-electroactive, Li 3v 2(PO 4) 3not only there is electro-chemical activity, and specific capacity compares LiCoPO 4height, can improve its specific capacity to a certain extent.Utilize LiCoPO 4high voltage ~ 4.8V, improve Li 3v 2(PO 4) 3operating voltage, improve its energy density.
LiCoPO 4with Li 3v 2(PO 4) 3compound, can make up mutually the other side's shortcoming, produces synergy, obtains the composite material xLiCoPO of electrochemical performance 4yLi 3v 2(PO 4) 3, its operating voltage is high, specific capacity is high, good rate capability, have extended cycle life, security performance is good, be a kind of new type lithium ion battery composite positive pole of high-energy-density, there is broad prospect of application.
Two of object of the present invention there are provided a kind of method preparing above-mentioned lithium ion battery composite cathode material, and concrete comprises the steps:
Mix containing cobalt, the precursor compound of vanadium or its crystalline hydrate with lithium source, phosphorus source, under inertia or reducing atmosphere, 550 ~ 850 DEG C sinter 4 ~ 24h, the lithium ion battery composite cathode material described in formation.
Further, mix by carbon source with containing cobalt, the precursor compound of vanadium or its crystalline hydrate, lithium source, phosphorus source, sinter under inertia or reducing atmosphere, form the lithium ion battery composite cathode material of carbon containing.
Preferably, described carbon source is at least one in acetylene black, graphite, Graphene, graphene oxide, carbon nano-tube, glucose, sucrose, citric acid, oxalic acid, ascorbic acid.
Preferably, the described precursor compound containing cobalt, vanadium is Co 2vO 4, Co 3v 2o 8, Co 2v 2o 7, CoV 2o 6in at least one.
Preferably, described Li source compound is at least one in lithium hydroxide, lithium carbonate, lithium acetate, lithium lactate, lithium nitrate, lithium oxalate, lithia, lithium phosphate, lithium dihydrogen phosphate.
Preferably, described P source compound is at least one in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium phosphate, lithium dihydrogen phosphate.
The preparation method of lithium ion battery composite cathode material of the present invention, precursor compound is simultaneously as cobalt source and vanadium source, molecule rank carries out chemical mixing, than by independent cobalt source and vanadium source mechanical mixture evenly, more be conducive to the performance of both composite positive poles cooperative effect of synthesizing, make the performance of composite positive pole more excellent.
Accompanying drawing explanation
In order to be illustrated more clearly in the technical scheme in the embodiment of the present invention, below the accompanying drawing used required in describing embodiment is briefly described, apparently, accompanying drawing for the present invention in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the XRD collection of illustrative plates of sample A1 in the embodiment of the present invention 1;
Fig. 2 is the first charge-discharge curve chart of sample A1 under different multiplying in the embodiment of the present invention 1.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is described in detail.
The present invention's raw material used all freely can be buied by market.
Embodiment 1
Take cobalt nitrate and ammonium metavanadate by the mol ratio 3:2 of Co and V, be dissolved in deionized water, then on electric furnace, boil 20 minutes, gained sedimentation and filtration, washing, in air, calcine 2h at 500 DEG C after drying, obtain Co 3v 2o 8presoma.By 3LiCoPO 4li 3v 2(PO 4) 3stoichiometric proportion take Co 3v 2o 8, lithium hydroxide and ammonium dihydrogen phosphate, add glucose (accounting for product quality 2% in carbon), above-mentioned raw materials is placed in ball grinder mechanical activation 2h, gained powder calcines 10h at 650 DEG C in argon gas, namely obtains the 3LiCoPO of carbon containing after cooling 4li 3v 2(PO 4) 3composite positive pole, sample is designated as A1.
Embodiment 2
Take cobalt acetate and three oxygen two vanadium by the mol ratio 1:1 of Co and V, mechanical activation 1h after mixing, gained powder calcines 1h at 700 DEG C in air, obtains Co 2v 2o 7presoma.By 2LiCoPO 4li 3v 2(PO 4) 3stoichiometric proportion take Co 2v 2o 7and lithium dihydrogen phosphate, above-mentioned raw materials is placed in ball grinder mechanical activation 5h, gained powder calcines 5h at 700 DEG C in argon hydrogen gaseous mixture (7vol% hydrogen), namely obtains 2LiCoPO after cooling 4li 3v 2(PO 4) 3composite positive pole, sample is designated as A2.
Embodiment 3
Take cobaltosic oxide and ammonium metavanadate by the mol ratio 1:2 of Co and V, mechanical activation 2h after mixing, gained powder calcines 5h at 400 DEG C in air, obtains CoV 2o 6presoma.By LiCoPO 4li 3v 2(PO 4) 3stoichiometric proportion take CoV 2o 6, lithium carbonate and phosphoric acid, adding oxalic acid (accounting for product quality 10% in carbon), take ethanol as dispersant, above-mentioned raw materials is placed in ball grinder mechanical activation 1h, by gained slurry drying, then in nitrogen, calcine 24h at 550 DEG C, after cooling, namely obtain the LiCoPO of carbon containing 4li 3v 2(PO 4) 3composite positive pole, sample is designated as A3.
Embodiment 4
Take cobalt carbonate and ammonium metavanadate by the mol ratio 2:1 of Co and V, mechanical activation 0.5h after mixing, namely gained powder 550 DEG C of calcining 3h in air obtain Co 2vO 4presoma.By 4LiCoPO 4li 3v 2(PO 4) 3stoichiometric proportion take Co 2vO 4, lithium acetate and diammonium hydrogen phosphate, add graphene oxide (in product quality 0.1%), above-mentioned raw materials is placed in ball grinder mechanical activation 3h, gained powder calcines 4h at 850 DEG C in argon hydrogen gaseous mixture (5vol% hydrogen), namely obtains the 4LiCoPO of carbon containing after cooling 4li 3v 2(PO 4) 3composite positive pole, sample is designated as A4.
Comparative example 1
By LiCoPO 4stoichiometric proportion take cobaltosic oxide, lithium carbonate and ammonium dihydrogen phosphate, above-mentioned raw materials is placed in ball grinder mechanical activation 4h, gained powder calcines 12h at 700 DEG C in air, after cooling LiCoPO 4positive electrode, sample is designated as D1.
Comparative example 2
By Li 3v 2(PO 4) 3stoichiometric proportion take vanadic oxide, lithium carbonate, ammonium dihydrogen phosphate, add glucose (accounting for product quality 2% in carbon), above-mentioned raw materials is placed in ball grinder mechanical activation 4h, gained powder calcines 12h at 700 DEG C in argon gas, namely obtains the Li of carbon containing after cooling 3v 2(PO 4) 3positive electrode, sample is designated as D2.
The properties of sample contrast prepared in each implementation column of table 1
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be realized in other specific forms.Therefore, no matter from which point, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention is limited by claims instead of above-mentioned explanation, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.
In addition, be to be understood that, although this specification is described according to execution mode, but not each execution mode only comprises an independently technical scheme, this narrating mode of specification is only for clarity sake, those skilled in the art should by specification integrally, and the technical scheme in each embodiment also through appropriately combined, can form other execution modes that it will be appreciated by those skilled in the art that.

Claims (10)

1. a lithium ion battery composite cathode material, is characterized in that: structural formula is xLiCoPO 4yLi 3v 2(PO 4) 3, described x and y meets x:y=50:1 ~ 1:10.
2. lithium ion battery composite cathode material according to claim 1, is characterized in that: described x and y meets x:y=20:1 ~ 1:2.
3. lithium ion battery composite cathode material according to claim 1 and 2, is characterized in that: be added with electric conducting material in described lithium ion battery composite cathode material.
4. lithium ion battery composite cathode material according to claim 3, is characterized in that: described electric conducting material is conductive carbon.
5. prepare a method for the lithium ion battery composite cathode material described in any one of claim 1 ~ 4, it is characterized in that, comprise the steps:
Mix containing cobalt, the precursor compound of vanadium or its crystalline hydrate with lithium source, phosphorus source, under inertia or reducing atmosphere, 550 ~ 850 DEG C sinter 4 ~ 24h, the lithium ion battery composite cathode material described in formation.
6. method according to claim 5, it is characterized in that: mix by carbon source with containing cobalt, the precursor compound of vanadium or its crystalline hydrate, lithium source, phosphorus source, sinter under inertia or reducing atmosphere, form the lithium ion battery composite cathode material of carbon containing.
7. method according to claim 6, is characterized in that: described carbon source is at least one in acetylene black, graphite, Graphene, graphene oxide, carbon nano-tube, glucose, sucrose, citric acid, oxalic acid, ascorbic acid.
8. the method according to claim 5 or 6, is characterized in that: the described precursor compound containing cobalt, vanadium is Co 2vO 4, Co 3v 2o 8, Co 2v 2o 7, CoV 2o 6in at least one.
9. the method according to claim 5 or 6, is characterized in that: described lithium source is at least one in lithium hydroxide, lithium carbonate, lithium acetate, lithium lactate, lithium nitrate, lithium oxalate, lithia, lithium phosphate, lithium dihydrogen phosphate.
10. the method according to claim 5 or 6, is characterized in that: described phosphorus source is at least one in phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, lithium phosphate, lithium dihydrogen phosphate.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108110242A (en) * 2017-12-19 2018-06-01 宁波高新区锦众信息科技有限公司 A kind of preparation method of lithium ion battery nickel manganese cobalt composite material
CN109088043A (en) * 2017-06-14 2018-12-25 中南大学 A kind of lithium sulphur-lithium ion hybrid battery and lithium sulphur-lithium ion hybrid battery positive electrode and preparation method thereof
CN109516504A (en) * 2018-11-26 2019-03-26 广东工业大学 A kind of porous hexa-prism pyrovanadic acid cobalt and its preparation method and application

Citations (1)

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Publication number Priority date Publication date Assignee Title
CN103762360A (en) * 2014-01-18 2014-04-30 天津理工大学 Preparation of lithium cobalt phosphate-lithium vanadium phosphate composite positive electrode material for lithium ion battery

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CN103762360A (en) * 2014-01-18 2014-04-30 天津理工大学 Preparation of lithium cobalt phosphate-lithium vanadium phosphate composite positive electrode material for lithium ion battery

Non-Patent Citations (2)

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Title
JUN-CHAO ZHENG等: ""Li3V2(PO4)3 cathode material synthesized by chemical reduction and lithiation method"", 《JOURNAL OF POWER SOURCES》 *
JUN-CHAO ZHENG等: ""LiFePO4 with enhanced performance synthesized by a novel synthetic route"", 《JOURNAL OF POWER SOURCES》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109088043A (en) * 2017-06-14 2018-12-25 中南大学 A kind of lithium sulphur-lithium ion hybrid battery and lithium sulphur-lithium ion hybrid battery positive electrode and preparation method thereof
CN108110242A (en) * 2017-12-19 2018-06-01 宁波高新区锦众信息科技有限公司 A kind of preparation method of lithium ion battery nickel manganese cobalt composite material
CN109516504A (en) * 2018-11-26 2019-03-26 广东工业大学 A kind of porous hexa-prism pyrovanadic acid cobalt and its preparation method and application

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