CN104393296B - 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 PDFInfo
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- CN104393296B CN104393296B CN201410736386.2A CN201410736386A CN104393296B CN 104393296 B CN104393296 B CN 104393296B CN 201410736386 A CN201410736386 A CN 201410736386A CN 104393296 B CN104393296 B CN 104393296B
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- lithium
- ion battery
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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
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- 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 discloses preparation method for a lithium ion battery composite positive electrode material. Precursor compounds containing cobalt and vanadium or crystalline hydrate of the precursor compounds, a lithium source and a phosphorus source are mixed uniformly according to a formula of xLiCoPO4.yLi3V2(PO4)3, wherein x:y=(50:1) to (1:10). The mixture is sintered under the inert or reducing atmosphere at 550-850 DEG C for 4-24 hours, and thus the composite positive electrode material can be obtained. The precursor compounds containing cobalt and vanadium are at least one of co2vo4, co3v2o8, co2v2o7 and cov2o6. 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
Technical field
The invention belongs to field of lithium ion battery, it is related to a kind of anode material for lithium-ion batteries and preparation method thereof, specifically
It is related to a kind of lithium ion battery composite cathode material and preparation method thereof.
Background technology
In recent years, the compound limpo of olivine structural4(m=fe, mn, ni and co etc.) due to have theoretical capacity high,
The advantages of good reversibility, heat stability and safety are good, becomes the study hotspot of field of lithium ion battery anode.At these
In compound, licopo4It is considered as the very promising 5v level high-voltage anode material of one kind, because it has high specific energy
Density (～800wh kg-1), high running voltage (～4.8v vs.li/li+), high theoretical specific capacity (167mah g-1).
However, licopo4There is very low electronic conductivity and lithium ion diffusion rate so that its chemical property is poor.
Currently to licopo4Focusing on of study on the modification improves its electronic conductivity and lithium ion diffusion rate two
Aspect, main path has Surface coating electronic conductor (as conductive carbon, conducting metal), ion bulk phase-doped modified (magnesium ion, manganese
Ion, nickel ion, iron ion, vanadium ion, ruthenium ion etc.), or micronized particles.Although these methods make licopo4Electricity
Chemical property makes moderate progress, but also needs to more effective method of modifying to commercialization.
li3v2(po4)3It is the another important member in phosphate system positive electrode.Have a safety feature because it has,
The features such as with low cost, Stability Analysis of Structures, chemical property are preferable, causes the extensive concern of researcher in recent years.li3v2(po4)3
Theoretical specific capacity height (～197mah g-1), and lithium ion diffusion rate is big, good rate capability, because it has special three
Dimension ion channel, lithium ion can soon embedded in crystal and abjection.Although li3v2(po4)3Have preferable high rate performance and
Higher theoretical specific capacity, but its average working voltage is relatively low, its have three working voltage platform (～3.55v,
3.6v and 4.0v), average working voltage is only～3.8v (vs.li/li+), which limits its energy density.
Content of the invention
In view of this, an object of the present invention is to provide a kind of raising licopo4Energy while electric conductivity and capacity
Improve li3v2(po4)3Running voltage, the lithium ion battery composite cathode material of energy density.
Specifically, the following technical scheme of present invention offer:
The lithium ion battery composite cathode material of the present invention, structural formula is xlicopo4·yli3v2(po4)3, described x and y
Meet x:y=50:1～1:10.
Preferably, described x and y meets x:y=20:1～1:2.
Further, it is added with conductive material in described lithium ion battery composite cathode material.
Preferably, described conductive material is conductive carbon.
Use li3v2(po4)3Fast ion conduction and high power capacity to licopo4Material is modified, and improves licopo4's
Electric conductivity, specific capacity and high rate performance；Use licopo4High voltage to li3v2(po4)3Modification, improves li3v2(po4)3Energy
Density.I.e. using the li with nascion structure3v2(po4)3It is the advantage of fast lithium ion conductor (lithium ion transport speed is fast),
To improve licopo4Ionic conductivity；And compared with the fast-ionic conductor of non-electroactive, li3v2(po4)3Not only have
Electro-chemical activity, and specific capacity compares licopo4Height, can improve its specific capacity to a certain extent.Using licopo4High voltage
～4.8v, to improve li3v2(po4)3Running voltage, improve its energy density.
licopo4With li3v2(po4)3Compound, other side's shortcoming can be made up mutually, produce synergism, obtain electrochemistry
The excellent composite xlicopo of energy4·yli3v2(po4)3, its running voltage height, specific capacity height, good rate capability, circulation longevity
Order length, have a safety feature, be a kind of new type lithium ion battery composite positive pole of high-energy-density, before there is wide application
Scape.
The second object of the present invention there are provided a kind of method preparing above-mentioned lithium ion battery composite cathode material,
Specifically comprise the steps:
To mix homogeneously with lithium source, phosphorus source containing cobalt, the precursor compound of vanadium or its crystalline hydrate, in inertia or reduction
Property atmosphere under 550～850 DEG C of sintering 4～24h, form described lithium ion battery composite cathode material.
Further, mix all by carbon source with containing cobalt, the precursor compound of vanadium or its crystalline hydrate, lithium source, phosphorus source
Even, sinter under inertia or reducing atmosphere, form the lithium ion battery composite cathode material of carbon containing.
Preferably, described carbon source is acetylene black, graphite, Graphene, graphene oxide, CNT, glucose, sugarcane
At least one in sugar, citric acid, oxalic acid, ascorbic acid.
Preferably, the described precursor compound containing cobalt, vanadium is co2vo4、co3v2o8、co2v2o7、cov2o6In extremely
Few one kind.
Preferably, described Li source compound be Lithium hydrate, lithium carbonate, lithium acetate, EINECS 212-761-8, lithium nitrate, lithium oxalate,
At least one in lithium oxide, lithium phosphate, lithium dihydrogen phosphate.
Preferably, described P source compound be phosphoric acid, triammonium phosphate, ammonium dihydrogen phosphate, diammonium phosphate, lithium phosphate,
At least one in lithium dihydrogen phosphate.
The preparation method of the lithium ion battery composite cathode material of the present invention, precursor compound is simultaneously as cobalt source and vanadium
Source, carries out chemical mixing in molecule rank, and ratio by single cobalt source with vanadium source mechanical mixture evenly, is more beneficial for synthesis
The performance of both composite positive poles cooperative effect is so that the performance of composite positive pole is more excellent.
Brief description
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, will make to required in embodiment description below
Accompanying drawing be briefly described it should be apparent that, below describe in accompanying drawing for the present invention be only the present invention one
A little embodiments, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to these
Accompanying drawing obtains other 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 first charge-discharge curve chart under different multiplying for the sample a1 in the embodiment of the present invention 1.
Specific embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, detailed retouching is carried out to the technical scheme in the embodiment of the present invention
State.
Raw material used by the present invention all freely can be buied by market.
Embodiment 1
Weigh cobalt nitrate and ammonium metavanadate by mol ratio 3:2 of co and v, be dissolved in deionized water, then boil on electric furnace
Boiling 20 minutes, gained precipitation filters, washing, is dried and calcines 2h at 500 DEG C of in the air, obtains final product co3v2o8Presoma.Press
3licopo4·li3v2(po4)3Stoichiometric proportion weigh co3v2o8, Lithium hydrate and ammonium dihydrogen phosphate, add glucose (with
Carbon accounts for product quality 2% and counts), above-mentioned raw materials are placed in mechanical activation 2h in ball grinder, gained powder 650 DEG C in the argon at forge
Burn 10h, after cooling, obtain final product the 3licopo of carbon containing4·li3v2(po4)3Composite positive pole, sample is designated as a1.
Embodiment 2
Weigh cobalt acetate and three oxygen two vanadium, mechanical activation 1h after mixing by mol ratio 1:1 of co and v, gained powder is in sky
Calcine 1h at 700 DEG C in gas, obtain final product co2v2o7Presoma.By 2licopo4·li3v2(po4)3Stoichiometric proportion weigh
co2v2o7And lithium dihydrogen phosphate, above-mentioned raw materials are placed in mechanical activation 5h in ball grinder, gained powder is in argon hydrogen gaseous mixture
Calcine 5h at 700 DEG C in (7vol% hydrogen), after cooling, obtain final product 2licopo4·li3v2(po4)3Composite positive pole, sample is remembered
For a2.
Embodiment 3
Weigh Cobalto-cobaltic oxide and ammonium metavanadate by mol ratio 1:2 of co and v, mechanical activation 2h after mixing, gained powder
Calcine 5h at 400 DEG C of in the air, obtain final product cov2o6Presoma.By licopo4·li3v2(po4)3Stoichiometric proportion weigh
cov2o6, lithium carbonate and phosphoric acid, add oxalic acid (accounting in terms of product quality 10% by carbon), with ethanol as dispersant, above-mentioned raw materials put
Mechanical activation 1h in ball grinder, by gained slurry drying, then 550 DEG C in the nitrogen at calcine 24h, obtain final product carbon containing after cooling
Licopo4·li3v2(po4)3Composite positive pole, sample is designated as a3.
Embodiment 4
Weigh cobalt carbonate and ammonium metavanadate by mol ratio 2:1 of co and v, mechanical activation 0.5h after mixing, gained powder in
550 DEG C of calcining 3h of in the air obtain final product co2vo4Presoma.By 4licopo4·li3v2(po4)3Stoichiometric proportion weigh co2vo4、
Lithium acetate and diammonium phosphate, add graphene oxide (in terms of product quality 0.1%), above-mentioned raw materials are placed in machine in ball grinder
Tool activates 3h, gained powder 850 DEG C in the argon hydrogen gaseous mixture (5vol% hydrogen) at calcine 4h, obtain final product carbon containing after cooling
4licopo4·li3v2(po4)3Composite positive pole, sample is designated as a4.
Comparative example 1
By licopo4Stoichiometric proportion weigh Cobalto-cobaltic oxide, lithium carbonate and ammonium dihydrogen phosphate, above-mentioned raw materials are placed in
Mechanical activation 4h in ball grinder, gained powder calcines 12h at 700 DEG C of in the air, after cooling licopo4Positive electrode, sample
Product are designated as d1.
Comparative example 2
By li3v2(po4)3Stoichiometric proportion weigh vanadic anhydride, lithium carbonate, ammonium dihydrogen phosphate, add glucose
(being accounted in terms of product quality 2% by carbon), above-mentioned raw materials are placed in mechanical activation 4h in ball grinder, and gained powder is 700 DEG C in argon
Lower calcining 12h, obtains final product the li of carbon containing after cooling3v2(po4)3Positive electrode, sample is designated as d2.
The properties of sample contrast that table 1 is prepared in respectively implementing to arrange
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, the present invention can be realized in other specific forms.Therefore, no matter
From the point of view of which point, embodiment all should be regarded as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all in the implication and scope of the equivalency of claim by falling
Change is included in the present invention.
Moreover, it will be appreciated that although this specification is been described by according to embodiment, not each embodiment only wraps
Containing an independent technical scheme, only for clarity, those skilled in the art should for this narrating mode of description
Using description as an entirety, the technical scheme in each embodiment can also form those skilled in the art through appropriately combined
Understandable other embodiment.
Claims (5)
1. a kind of method preparing lithium ion battery composite cathode material is it is characterised in that comprise the steps:
The structural formula of described lithium ion battery composite cathode material is xlicopo4·yli3v2(po4)3, described x and y meet x:
Y=50:1～1:10；
To mix homogeneously with lithium source, phosphorus source containing cobalt, the precursor compound of vanadium or its crystalline hydrate, in inertia or reproducibility gas
Under atmosphere, 550～850 DEG C of sintering 4～24h, form described lithium ion battery composite cathode material；The described forerunner containing cobalt, vanadium
Body compound is co2vo4、co3v2o8、co2v2o7、cov2o6In at least one.
2. method according to claim 1 it is characterised in that: by carbon source and containing cobalt, the precursor compound of vanadium or its knot
Brilliant hydrate, lithium source, phosphorus source mix homogeneously, sinter under inertia or reducing atmosphere, and the lithium ion battery forming carbon containing is combined
Positive electrode.
3. method according to claim 2 it is characterised in that: described carbon source be acetylene black, graphite, Graphene, oxidation
At least one in Graphene, CNT, glucose, sucrose, citric acid, oxalic acid, ascorbic acid.
4. method according to claim 1 and 2 it is characterised in that: described lithium source be Lithium hydrate, lithium carbonate, acetic acid
At least one in lithium, EINECS 212-761-8, lithium nitrate, lithium oxalate, lithium oxide, lithium phosphate, lithium dihydrogen phosphate.
5. method according to claim 1 and 2 it is characterised in that: described phosphorus source be phosphoric acid, triammonium phosphate, di(2-ethylhexyl)phosphate
At least one in hydrogen ammonium, diammonium phosphate, lithium phosphate, lithium dihydrogen phosphate.
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| 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 |
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