CN103928682A - Lithium cobalt phosphate cathode material and preparation method thereof - Google Patents

Lithium cobalt phosphate cathode material and preparation method thereof Download PDF

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Publication number
CN103928682A
CN103928682A CN201410158992.0A CN201410158992A CN103928682A CN 103928682 A CN103928682 A CN 103928682A CN 201410158992 A CN201410158992 A CN 201410158992A CN 103928682 A CN103928682 A CN 103928682A
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CN
China
Prior art keywords
cobalt
lithium
positive electrode
sodium
cobalt phosphate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410158992.0A
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Chinese (zh)
Inventor
毛文峰
张新河
唐致远
李中延
郑新宇
汤春微
丁玉茹
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Mcnair Technology Co Ltd
Dongguan Mcnair New Power Co Ltd
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Mcnair Technology Co Ltd
Dongguan Mcnair New Power Co Ltd
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Application filed by Mcnair Technology Co Ltd, Dongguan Mcnair New Power Co Ltd filed Critical Mcnair Technology Co Ltd
Priority to CN201410158992.0A priority Critical patent/CN103928682A/en
Publication of CN103928682A publication Critical patent/CN103928682A/en
Pending legal-status Critical Current

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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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/26—Phosphates
    • C01B25/45—Phosphates containing plural metal, or metal and ammonium
    • 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
    • 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)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to the technical field of lithium ion batteries, and particularly relates to a lithium cobalt phosphate cathode material and a preparation method thereof. The chemical general formula of the lithium cobalt phosphate cathode material provided by the invention is Li1-xNaxCoPO4; compared with an existing lithium cobalt phosphate cathode material, the lithium cobalt phosphate cathode material provided by the invention not only has good cycling stability, but also has excellent rate capability.

Description

A kind of cobalt phosphate lithium positive electrode and preparation method thereof
Technical field
The present invention relates to technical field of lithium ion, particularly relate to a kind of cobalt phosphate lithium positive electrode and preparation method thereof.
Background technology
The progress in modern epoch, the continuous miniaturization of consuming device, multifunction, the requirement for battery accordingly is also improving constantly.Lithium ion battery has many advantages: voltage platform is high, and specific capacity is high, has extended cycle life, and self discharge is low, and memory-less effect etc. have huge application prospect on electric automobile and energy storage device.
At present, high-energy-density, durable, high magnification (fast charging and discharging ability), cheapness, safety have become the target that lithium ion battery development is pursued.Owing to having specific capacity, be LiCoO 2the specific capacity of material twice, cobalt phosphate lithium positive electrode is considered to the ideal material of high-energy electrokinetic cell of future generation.But cobalt phosphate lithium positive electrode exists the problems such as conductivity is low, be difficult to meet practical application.And be coated with doping, it is the main method that improves positive electrode performance.
Summary of the invention
In order to address the above problem, the object of the invention is to, provide a kind of good cycling stability, the cobalt phosphate lithium positive electrode that high rate performance is good.
Two of object of the present invention is to provide a kind of simple, the preparation method of described cobalt phosphate lithium positive electrode.
The present invention is achieved through the following technical solutions:
A cobalt phosphate lithium positive electrode, the chemical general formula of described cobalt phosphate lithium positive electrode is Li 1-xna xcoPO 4; Wherein: 0≤X≤0.5.
The method of preparing described sodium doping phosphoric acid cobalt lithium anode material:
After first weighing respectively lithium salts, sodium salt, cobalt salt, microcosmic salt mixing with mol ratio Li:Na:Co:P=1-x:x:1:1, obtain mixture I;
In said mixture I, add solvent adjustment to rheology phase again, obtain mixture II;
After then said mixture II being dried, putting into temperature and be the Muffle furnace of 700～1000 ℃ calcines after 8～48 hours and obtains described cobalt phosphate lithium positive electrode; Mainly utilize airborne oxygen to originate as reactant, reactant needs at high temperature and the abundant haptoreaction of oxygen.
Wherein, 0≤X≤0.5.
Wherein, rheology is a kind of process of preparing noval chemical compound by rheology hybrid system mutually.By suitably mixing, add suitable quantity of water or other solvent to be modulated into solids and the even not stratified thick solid-liquid hybrid system-rheology phase system of liquid distribution reactant, then reaction obtains required product under proper condition.Material in rheology state generally chemically has complicated composition or structure; The character that demonstrates solid on mechanics demonstrates again the character of liquid, in other words conj.or perhaps like solid non-solid, like the non-liquid of liquid; On physical composition, be both to have comprised solid particle also to comprise liquid substance, can flow or the slow mobile uniform a kind of complication system of macroscopic view.
The homogeneous of solid particle and liquid substance is mixed to the advantage as rheological body: the surface area of solid particle can be effectively utilized, tight with fluid contact, evenly, heat exchange is good, there will not be local overheating phenomenon, and temperature is easy to regulate.Many materials can show excess of export concentration phenomenon and new response characteristic in this state.Rheological phase reaction be a kind of energy-conservation, efficient, subtract dirty green chemical synthetic route.
Specific practice of the present invention is: add appropriate solvent, control material viscosity at certain limit 3000～20000cp.
Preferably, microcosmic salt is a kind of in phosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate.
Preferably, cobalt salt is a kind of in cobalt acetate, cobalt oxalate, cobaltous sulfate, cobalt nitrate, cobalt chloride.
Preferably, lithium salts is a kind of in lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium chloride.
The present invention tends to use lithium nitrate, because lithium nitrate, about the 200 ℃ first meltings of meeting, makes fully contact between raw material, reduces the reaction time, reduces reaction temperature, energy savings.
Preferably, sodium salt is a kind of in sodium nitrate, sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium chloride.
Preferably, solvent is at least one in ethanol, deionized water, 1-METHYLPYRROLIDONE (NMP), acetone.
The present invention is mainly lithium position sodium-doped, uses part sodium to replace the elemental lithium in cobalt phosphate lithium.Its reason is: a. lithium and sodium belong to the first major element (the first major element sequence Li Na K ...), only have sodium ion radius to approach lithium ion radius most, if replace the elemental lithium in cobalt phosphate lithium material, sodium is first-selected.B. sodium metal, than lithium metal low price, is conducive to material cost and reduces.
The invention has the beneficial effects as follows:
(1), because sodium ion radius is greater than lithium ion radius, therefore, de-/embedding that the cobalt phosphate lithium positive electrode after sodium doping is more conducive to lithium ion, the conductivity of corresponding sodium doping phosphoric acid cobalt lithium can get a promotion.
(2), the present invention uses Rheological Phase Method to prepare sodium doping lithium-rich anode material.Rheological Phase Method is to use solvent by a kind of state between liquid phase and solid phase of raw material furnishing, the method has the following advantages: with respect to liquid phase method, reduce solvent load, shorten time, the energy except desolventizing, thereby economize on resources the energy, improve material preparation efficiency; With respect to solid phase method, batch mixing is more even, and does not need the techniques such as ball milling, reduces energy consumption.
(3), because the present invention introduces low-cost sodium salt, reduced expensive lithium salts consumption, thereby reduced the cost of cobalt phosphate lithium material.
Accompanying drawing explanation
Fig. 1 is the charging and discharging curve figure of cobalt phosphate lithium material in the present invention and prior art.
Concrete execution mode
Below in conjunction with embodiment, the present invention is described in further detail, to help those skilled in the art, understands the present invention.
Embodiment 1:
With mol ratio Li:Na:Co:P=0.98:0.02:1:1, weigh respectively Li 2cO 3, Na 2cO 3, Co (NO 3) 2, NH 4h 2pO 4, add appropriate ethanol to regulate raw material to rheology phase, stirring at room is calcined and within 16 hours, is obtained sodium doping phosphoric acid cobalt lithium anode material Li to putting into after dry at 800 ℃ of Muffle furnaces 0.98na 0.02coPO 4.
Embodiment 2:
With mol ratio Li:Na:Co:P=0.9:0.1:0.5:1.5, weigh respectively Li 2cO 3, Na 2cO 3, Co (NO 3) 2, NH 4h 2pO 4, add appropriate ethanol to regulate raw material to rheology phase, stirring at room is calcined and within 16 hours, is obtained sodium doping phosphoric acid cobalt lithium anode material Li to putting into after dry at 800 ℃ of Muffle furnaces 0.9na 0.1coPO 4.
Embodiment 3:
With mol ratio Li:Na:Co:P=0.9:0.1:0.5:1.5, weigh respectively LiOH, NaOH, Co (CH 3cOO) 2, H 3pO 4, add appropriate amount of deionized water to regulate raw material to rheology phase, stirring at room is calcined and within 16 hours, is obtained sodium doping phosphoric acid cobalt lithium anode material Li to putting into after dry at 800 ℃ of Muffle furnaces 0.9na 0.1coPO 4.
Above-described embodiment, is preferred embodiment of the present invention, is not used for limiting the scope of the present invention, and the equivalence of being done with the feature described in the claims in the present invention and principle therefore all changes or modifies, within all should being included in the claims in the present invention scope.
By Fig. 1 charging and discharging curve comparison diagram, can be found out, after cobalt phosphate lithium sample sodium contaminated, material polarization obviously reduces, and its specific discharge capacity is by unadulterated 90mAh g -1increase to the 98mAh g after doping -1, illustrate that sodium is doped with the chemical property that helps promote cobalt phosphate lithium positive electrode.

Claims (7)

1. a cobalt phosphate lithium positive electrode, is characterized in that, the chemical general formula of described cobalt phosphate lithium positive electrode is Li 1-xna xcoPO 4; Wherein: 0≤X≤0.5.
2. the method for preparing the positive electrode of cobalt phosphate lithium described in claim 1, is characterized in that,
After first weighing respectively lithium salts, sodium salt, cobalt salt, microcosmic salt mixing with mol ratio Li:Na:Co:P=1-x:x:1:1, obtain mixture I;
In said mixture I, add solvent adjustment to rheology phase again, obtain mixture II;
After then said mixture II being dried, putting into temperature and be the Muffle furnace of 700～1000 ℃ calcines after 8～48 hours and obtains described cobalt phosphate lithium positive electrode;
Wherein, 0≤X≤0.5.
3. the preparation method of cobalt phosphate lithium positive electrode described in claim 2, is characterized in that, microcosmic salt is a kind of in phosphoric acid, ammonium dihydrogen phosphate, ammonium hydrogen phosphate.
4. the preparation method of cobalt phosphate lithium positive electrode described in claim 2, is characterized in that, cobalt salt is a kind of in cobalt acetate, cobalt oxalate, cobaltous sulfate, cobalt nitrate, cobalt chloride.
5. the preparation method of cobalt phosphate lithium positive electrode described in claim 2, is characterized in that, lithium salts is a kind of in lithium nitrate, lithium carbonate, lithium oxalate, lithium acetate, lithium chloride.
6. the preparation method of cobalt phosphate lithium positive electrode described in claim 2, is characterized in that, sodium salt is a kind of in sodium nitrate, sodium carbonate, sodium acid carbonate, sodium acetate, sodium oxalate, sodium chloride.
7. the preparation method of cobalt phosphate lithium positive electrode described in claim 2, is characterized in that, solvent is at least one in ethanol, deionized water, 1-METHYLPYRROLIDONE, acetone.
CN201410158992.0A 2014-04-18 2014-04-18 Lithium cobalt phosphate cathode material and preparation method thereof Pending CN103928682A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115667135A (en) * 2020-05-25 2023-01-31 Fdk株式会社 Method for producing lithium cobalt pyrophosphate and method for producing solid battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100074822A1 (en) * 2007-04-20 2010-03-25 Sung Yoon Chung Method for making nanoparticles of lithium transition metal phosphates
CN101807691A (en) * 2010-04-19 2010-08-18 湘西自治州矿产与新材料技术创新服务中心 Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery
CN102709552A (en) * 2012-05-22 2012-10-03 吉首大学 Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery
CN103400968A (en) * 2013-08-09 2013-11-20 天津巴莫科技股份有限公司 Lithium manganese phosphate-capacitance carbon composite material, preparation method thereof, and lithium ion capacitance battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100074822A1 (en) * 2007-04-20 2010-03-25 Sung Yoon Chung Method for making nanoparticles of lithium transition metal phosphates
CN101807691A (en) * 2010-04-19 2010-08-18 湘西自治州矿产与新材料技术创新服务中心 Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery
CN102709552A (en) * 2012-05-22 2012-10-03 吉首大学 Preparation method of iron-doped lithium vanadium oxygen phosphate (LiVOPO4) positive material for lithium ion battery
CN103400968A (en) * 2013-08-09 2013-11-20 天津巴莫科技股份有限公司 Lithium manganese phosphate-capacitance carbon composite material, preparation method thereof, and lithium ion capacitance battery

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115667135A (en) * 2020-05-25 2023-01-31 Fdk株式会社 Method for producing lithium cobalt pyrophosphate and method for producing solid battery

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