CN102779995A - Phosphoric acid cathode material of lithium battery - Google Patents

Phosphoric acid cathode material of lithium battery Download PDF

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Publication number
CN102779995A
CN102779995A CN2011101250462A CN201110125046A CN102779995A CN 102779995 A CN102779995 A CN 102779995A CN 2011101250462 A CN2011101250462 A CN 2011101250462A CN 201110125046 A CN201110125046 A CN 201110125046A CN 102779995 A CN102779995 A CN 102779995A
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China
Prior art keywords
phosphoric acid
lithium battery
positive electrode
phosphate
cathode material
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CN2011101250462A
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Chinese (zh)
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汤卫平
解晶莹
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Shanghai Institute of Space Power Sources
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Shanghai Institute of Space Power Sources
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Priority to CN2011101250462A priority Critical patent/CN102779995A/en
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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 relates to a phosphoric acid cathode material of a lithium battery. The phosphoric acid cathode material is represented by LixMyPO4(POz)q, wherein M=Fe, Mn, V or a mixture thereof, x is no larger than 0.8 and no less than 1.4, y is no larger than 0.8 and no less than 1.2, z is no larger than 3.5 and no less than 0.33, q is no larger than 0.4 and no less than 0, and POz is pyrophosphate, phosphite, metaphosphate, cyclic monophosphate or a mixture thereof. The invention further relates to a preparation method of the cathode material. According to the invention, by introducing POz in the cathode material, the conductivity and ion diffusion performance of the cathode material are effectively raised, and the lithium battery assembled with the cathode material displays excellent charge and discharge capacity.

Description

A kind of lithium battery phosphoric acid series positive electrode
Technical field
The present invention relates to the battery production field, be specifically related to a kind of positive electrode that is used to produce lithium battery; In addition, the invention still further relates to the preparation method of this positive electrode.
Background technology
Existing phosphoric acid series (LiMPO 4M=Fe, Mn, V etc. or its mixture) positive electrode; Because its conduction and ions diffusion performance are inferior, can not give full play to the charge-discharge performance of these materials like LiFePO4, lithium manganese phosphate, phosphoric acid ferrimanganic lithium and phosphoric acid ferrovanadium lithium etc. when using as the positive electrode of lithium battery.In addition, it is a lot of that the charging voltage of this positive electrode exceeds discharge voltage, is illustrated in mws polarization serious in the charge and discharge process and distortion.
In order to improve the charge-discharge performance of these materials, the different metallic element that in these phosphoric acid series positive electrodes, mixes usually, like Mo, Nd, Ti, Mn, Ni, Mg wait and improve its conductivity and ionic diffusion coefficient.
Summary of the invention
To the above-mentioned deficiency of prior art, technical problem to be solved by this invention is to provide conduction and ions diffusion ability excellence, structural stability, and charge-discharge performance obtains the lithium battery phosphoric acid series positive electrode of very big optimization; And the preparation method of this positive electrode proposed.
In order to solve the problems of the technologies described above, a kind of lithium battery phosphoric acid series positive electrode provided by the invention, its composition can be characterized by Li xM yPO 4(PO z) q, M=Fe wherein, Mn, V etc. or its mixture, 0.8>=x>=1.4,0.8>=y>=1.2,3.5>=z>=0.33,0.4>=q>=0, PO zBe pyrophosphate, cycli phosphate root etc., or the mixture of aforementioned these acid groups.Through introducing pyrophosphate, cycli phosphate root, can reach Li/Fe mol ratio and Li/P mol ratio in the adjustment product composition, reach the purpose of optimizing product lithium diffusion coefficient.
The preparation of the aforementioned positive electrode of the present invention can prepare with solid phase method or one step of coprecipitation method, or through product M between preparation wherein yPO 4(PO z) q, mix being fired into Li again with lithium salts xM yPO 4(PO z) q
Be equipped with Li with the single step reaction legal system xM yPO 4(PO z) qThe time, with a kind of in ball milling or mortar mixing lithium salts, molysite, phosphate and pyrophosphoric acid and the cycli phosphate or several, under high temperature inert atmosphere, burn till its mixture and obtain.The raw material of introducing lithium, M, phosphorus can be a kind of or several lithiums, M, the raw material of phosphorus or their compound of ferric nitrate, ferric oxalate, ferric phosphate, ferrous phosphate, lithium phosphate, lithium hydrogen phosphate, phosphoric acid hydrogen ammonia, lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate etc., only otherwise the raw material of bringing impurity into all can in.The incorporation time of using ball milling or mortar for several hours after 24 hours, under the 500-700 temperature, burn till crystallization.In mixed process, add an amount of carbonized stock such as sugar and can obtain carbon parcel lithium iron phosphate positive material.
The preparation of the aforementioned positive electrode of the present invention can also be used the preparation of intermediate product method.The typical method of intermediate product method comprises the steps: A, mixes certain density molysite, a kind of or several preparations M in phosphate and pyrophosphoric acid, cycli phosphate or these acid groups yPO 4(PO z) qMolysite can be a ferric sulfate, iron chloride, and its concentration is 0.2-2mol/l; The raw material of introducing phosphorus is mainly sodium phosphate, dibastic sodium phosphate, phosphoric acid ammonia, phosphoric acid hydrogen ammonia etc., and concentration is 0.5-2mol/l.Part in these phosphate substitutes with pyrophosphoric acid and cycli phosphate can reach the purpose of in product, introducing pyrophosphoric acid and cycli phosphate root, and pyrophosphoric acid and cycli phosphate can directly add.After fully stirring, filter repeatedly, clean 3-4 all over after, drying can obtain nano combined intermediate product M yPO 4(PO z) qMixing speed during reaction is 50-800rmp; Reaction time is 30 minutes to 10 hours; Baking temperature 80-150 degree.B, under inert atmosphere the calcining M yPO 4(PO z) qCan obtain high crystalline phosphoric acid series positive electrode with the mixture of lithium salts.With lithium compound mixing 2-24 hour, the Li/Fe mol ratio in the mixture was 0.9-1.18 with nano combined intermediate product; Yet in inert atmosphere, burn till mixture, inert atmosphere can be with N2 or Ar gas or N2 or the Ar gas of H2 gas that contains 3-10% to strengthen reducing atmosphere; Temperature is between the 450-700 degree.But synthesized high-performance carbon coats LiMPO thus 4Positive electrode.Through control and optimization firing temperature and temperature schedule, Li/P ratio and reducing atmosphere power and pyrophosphoric acid and cycli phosphate root can be optimized the crystalline texture of product, indexs such as control ratio surface area and particle diameter.Add carbonized stock such as sugar in the mixed process and can obtain carbon parcel lithium iron phosphate positive material.
Use Li of the present invention xM yPO 4(PO z) qPositive electrode assembling lithium battery method is: with above-mentioned synthetic Li xM yPO 4(PO z) qProcessing cathode film, is negative pole with the graphite film, and the multilayer microporous film that PP and PE are compound is a barrier film, 1mol dm -3LiFP 6In EC-DEC (1: 1) assembles lithium battery, and Test Example subsequently will prove, use Li of the present invention xM yPO 4(PO z) qThe lithium battery of positive electrode assembling has high discharge capacity and stable cycle charge discharge electrical property.
With respect to prior art, Li provided by the invention xM yPO 4(PO z) qPositive electrode passes through at LiMPO 4Import pyrophosphate in the structure, or orthophosphite, or metaphosphoric acid radical, or the cycli phosphate root, or these ions more than two kinds.Adjusting crystalline texture through the composition of regulating the phosphate radical in these materials improves the electricity of LiFePO4 and leads and the ions diffusion performance; In crystalline texture, import the hole; Thereby reach the conductivity that improves these positive electrodes; Structural stability and ions diffusion ability, the purpose of optimization charge-discharge performance.Li provided by the invention xM yPO 4(PO z) qThe entire synthesis process of positive electrode is simple to operate, and controllability is strong, and the conductivity and the ions diffusion performance of excellence arranged with the lithium iron phosphate positive material of this method preparation.Lithium battery with the assembling of the positive electrode of fabrication techniques of the present invention has high discharge capacity and stable cycle charge discharge electrical property, and is with low cost, uses in extensive rangely, is beneficial to popularization.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.These embodiment are interpreted as only being used to the present invention is described and are not used in restriction protection scope of the present invention.After the content of having read the present invention's record, those skilled in the art can do various changes or modification to the present invention, and these equivalences change and modify and fall into claim of the present invention institute restricted portion equally.
Embodiment 1
Mixed 0.41mol/l Fe 2(SO 4) 331.2ml with 0.861mol/l NaPO 4Solution 62.4ml and 1mol/l Na 4P 2O 7Among the solution 4.6ml, used mixing speed is 450rmp;
Stir after 2 hours and to filter, and filtration product is cleaned with distilled water, filter repetition 3 times after, at 0.001mol/l H 4P 2O 7Handle in the solution after 30 minutes, dry 4 hours of 100 degree obtain sample 1.
Sample 1 is prone to filter very much, does not lump after the drying and need not pulverize.The x-line diffracted ray figure of sample 1 shows that the compound that obtains is non-crystallne phosphoric acid iron lithium.
Sample 1 and LiCH 3COOH 2O and C 12H 22O 11With behind 1: 1.04: 0.014 molar ratio weighing, after mixed number on the automatic mixer hour, containing 3%H 2N 2Atmosphere in 350 degree burn till after 3 hours slowly cooling, obtain sample 2.After mixing 1 hour on the automatic mixer, containing 3%H to sample 2 once more 2N 2600 degree burn till slowly cooling after 5 hours in the atmosphere, obtain sample 3.The x-line diffracted ray figure of sample 3 shows except the diffraction maximum of olivine structure lithium iron phosphate, to also have faint Li 4P 2O 7Diffraction maximum.
Test Example 1
With sample 3 is positive electrode, and the lithium metal is a negative pole, 1mol/l LiPF 6In EC-DEC (1: 1) is for the charging and discharging curve of electrolytical lithium battery shows, the discharge capacity first under the current density of 20mA/g is 155mAh/g, and has shown good cyclical stability; Discharge capacity under the current density of 1000mA/g is 98mAh/g, and has kept good cyclical stability.
Test row 2
Measured the lithium ion diffusion coefficient of sample 3 with electrochemical process.Its result is 4.1x10 -15Cm 2/ s is than the ferric phosphate diffusion coefficient (10 of bibliographical information -19Cm 2/ s the order of magnitude) exceeds about 4 one magnitude, shown high lithium ion diffusivity.

Claims (3)

1. a lithium battery phosphoric acid series positive electrode is characterized in that it consists of Li xM yPO 4(PO z) q, wherein: M is Fe, Mn, V, or its mixture, 0.8>=x>=1.4,0.8>=y>=1.2,3.5>=z>=0.33,0.4>=q>=0, PO zBe a kind of or two kinds and the above mixture in pyrophosphate, orthophosphite, metaphosphoric acid radical and the cycli phosphate root.
2. according to the said a kind of lithium battery phosphoric acid series positive electrode of claim 1; It is characterized in that; Mix lithium salts, molysite, phosphate with solid phase method or solwution method; With a kind of in pyrophosphoric acid, phosphorous acid, metaphosphoric acid and the cycli phosphate or several, under high temperature inert atmosphere, burn till its mixture, make lithium battery phosphoric acid series positive electrode.
3. according to the said a kind of lithium battery phosphoric acid series positive electrode of claim 1, it is characterized in that, comprise the steps:
A, mix a kind of in certain density molysite, phosphate and pyrophosphoric acid, phosphorous acid, metaphosphoric acid, cycli phosphate or these acid groups or several preparations M yPO 4(PO z) q
B, under inert atmosphere the calcining M yPO 4(PO z) qWith the mixture of lithium salts, make lithium battery phosphoric acid series positive electrode.
CN2011101250462A 2011-05-13 2011-05-13 Phosphoric acid cathode material of lithium battery Pending CN102779995A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024055517A1 (en) * 2022-09-13 2024-03-21 广东邦普循环科技有限公司 Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101212048A (en) * 2006-12-30 2008-07-02 比亚迪股份有限公司 Anode material of Li-ion secondary battery and battery containing the same
CN101610977A (en) * 2006-12-22 2009-12-23 尤米科尔公司 Synthesis of electroactive crystalline nanometer LiMnPO 4Powder
CN101628714A (en) * 2009-07-27 2010-01-20 深圳市德方纳米科技有限公司 Carbon-free nanoscale lithium iron phosphate and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101610977A (en) * 2006-12-22 2009-12-23 尤米科尔公司 Synthesis of electroactive crystalline nanometer LiMnPO 4Powder
CN101212048A (en) * 2006-12-30 2008-07-02 比亚迪股份有限公司 Anode material of Li-ion secondary battery and battery containing the same
CN101628714A (en) * 2009-07-27 2010-01-20 深圳市德方纳米科技有限公司 Carbon-free nanoscale lithium iron phosphate and preparation method thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2024055517A1 (en) * 2022-09-13 2024-03-21 广东邦普循环科技有限公司 Ferrophosphorus lithium-ion battery positive electrode material, and preparation method therefor and use thereof

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Application publication date: 20121114