CN104037409A - Preparation method for titanium-doped lithium vanadyl phosphate positive electrode material used for lithium ion battery - Google Patents

Preparation method for titanium-doped lithium vanadyl phosphate positive electrode material used for lithium ion battery Download PDF

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Publication number
CN104037409A
CN104037409A CN201310068456.7A CN201310068456A CN104037409A CN 104037409 A CN104037409 A CN 104037409A CN 201310068456 A CN201310068456 A CN 201310068456A CN 104037409 A CN104037409 A CN 104037409A
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lithium
titanium
ball
ion battery
vanadyl phosphate
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何则强
熊利芝
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Jishou University
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Jishou 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method for a titanium-doped lithium vanadyl phosphate positive electrode material used for a lithium ion battery. The nominal composition formula of the positive electrode material is LiTixV1-xOPO4, and the doping amount x is in a range of more than 0 and less than 0.1. The preparation method comprises the following steps: mixing a lithium source, a titanium source, a vanadium source and a phosphorus source; adding the obtained mixture into a ball milling medium and a dispersant and carrying out mixing and ball milling for 4 to 6 h so as to obtain rheological gelatinoid; drying the rheological gelatinoids at 60 to 80 DEG C for 2 h and carrying out grinding so as to obtain fine powder; and then carrying out sintering at 400 to 800 DEG C in a certain atmosphere for 6 to 10 h so as to obtain titanium-doped lithium vanadyl phosphate powder with the nominal composition formula of LiTixV1-xOPO4. According to the invention, a rheological phase process which can easily realize commercialized production is employed, simple mixing, ball milling and drying are carried out and heat treatment temperature and time are controlled so as to prepare the titanium-doped lithium vanadyl phosphate positive electrode material powder with good crystallinity and uniform components for a secondary lithium ion battery; and the initial discharge specific capacity of the positive electrode material powder at room temperature is greater than 140 mAh/g. Compared with pure lithium vanadyl phosphate, the titanium-doped lithium vanadyl phosphate positive electrode material powder provided by the invention substantially improves cycle performance, especially high rate performance, of a matrix and is suitable for industrialized production.

Description

The preparation method of titanium doped vanadyl phosphate lithium anode material for lithium ion battery
Technical field
The present invention relates to the preparation method of the titanium doped vanadyl phosphate lithium anode material of a kind of lithium ion battery.
Background technology
LiVOPO 4theoretical capacity reach 159 mAh/g, Stability Analysis of Structures, quite (being 3.8-3.9V with respect to lithium metal) of discharge voltage and other positive active material, but it is unlike LiFePO 4the same, when synthetic, not necessarily need reducing atmosphere.Although Li 3v 2 (pO 4) 3in transition metal phosphate, there is the highest theoretical specific capacity (197 mAh/g), but it have 3.6,3.7,4.1, four charge and discharge platform such as 4.6V, and the capacity of these platforms is difficult to whole performances in actual applications.LiVOPO 4only have a charge and discharge platform, capacity can be fully used.Meanwhile, the resource of vanadium is very abundant, the output rank third place in the world of China's vanadium, and also the price of vanadium is also much lower than cobalt, considers from material cost, and in China, research and development Li-V is that positive electrode compares LiCoO 2positive electrode has more practical significance.LiVOPO 4these advantages become LiCoO 2a potential replacer.
Literature research shows, LiVOPO 4the maximum bottleneck that is applied to lithium ion battery as positive electrode is LiVOPO 4the low and lithium ion of electronic conductivity diffusion coefficient is slow therein, and it is the same merely by LiVOPO to press conventional art 4mix with conductive auxiliary agent, be difficult to head it off.
We disclose lithium position sodium-doped and rear-earth-doped LiVOPO in patent CN101807691A and CN101841027A 4preparation method, but up to now, also do not find titanium doped LiVOPO 4the research report of positive electrode.
Summary of the invention
The object of the present invention is to provide the preparation method of a kind of lithium ion battery with titanium doped vanadyl phosphate lithium anode material, product has improved the basic electrical property of electrode material, proposition utilizes Rheological Phase Method to synthesize manganese doping type vanadyl phosphate lithium anode material, and technique is simple, is suitable for suitability for industrialized production.
The object of the invention is to realize as follows: titanium doped vanadyl phosphate lithium anode material for lithium ion battery, its nominal composition formula is LiTi xv 1-xoPO 4, wherein, doping scope 0 < x < 0.1.
In synthetic doped compound, the doping of iron is a kind of nominal composition amount, does not represent the actual final doping that enters oxygen lattice position.
Prepare the method for above lithium ion battery with titanium doped type vanadyl phosphate lithium anode material, it is to be combined to mode by the rheology after parent stock and alloy mixing and ball milling: lithium source, titanium source, He Lin source, vanadium source is by Li:Mn:V:P=1:x:(1-x): 1 amount of substance adds the container of mixing and ball milling than raw materials weighing, then add ball-milling medium and dispersant ball milling, mixing and ball milling time 4-6 hour, obtain rheology state jelly, 60-80 DEG C of dry 2h, grind to form fine powder, in certain atmosphere, count 6-10h in 400 DEG C of-800 DEG C of sintering again, obtain the titanium doped vanadyl phosphate powder for lithium of nominal composition formula.
Dispersant is one or more the mixture in deionized water, industrial alcohol, absolute ethyl alcohol, acetone.
The container of mixing and ball milling be corundum ball grinder, agate jar,, one in polyurethane ball-milling pot, nylon ball grinder, tungsten-carbide ball grinding jar.
Ball-milling medium is the one in zirconia ball, corundum ball, agate ball, stainless steel ball, polyurethane ball.
Lithium source is the one in lithium carbonate, lithium oxalate, lithium acetate, lithium hydroxide.
Vanadium source is the one of vanadic oxide, ammonium metavanadate.
Titanium source is the one in titanium dioxide, butyl titanate, titanium sulfate or organic titanium salt.
Phosphorus source is the one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
Protective atmosphere is the one in nitrogen, argon gas, and protective atmosphere air-flow velocity is 0.1-8.0 liter/min.
The present invention utilizes the Rheological Phase Method that is easy to commercially produce, through simple mixing and ball milling technique, by controlling heat treatment temperature and time, prepare that crystal property is good, the uniform titanium doped lithium ion battery vanadyl phosphate lithium anode material of composition, under room temperature, first discharge specific capacity is greater than 140mAh/g.Compared with pure phosphoric acid vanadyl lithium, the present invention has significantly improved particularly high rate capability of parent cycle performance, is applicable to suitability for industrialized production simultaneously.Can be widely used in button, cylindrical and square lithium ion battery and lithium-ion-power cell
The titanium doped vanadyl phosphate lithium that adopts the present invention to prepare is applicable to as the lithium ion battery of positive electrode the equipment that various mobile electronic devices maybe need mobile driven by energy, such as mobile phone, notebook computer, portable camera, electric bicycle, electric automobile, hybrid-electric car and energy storage device etc.
Embodiment
embodiment 1
Take and analyze pure level lithium carbonate 7.389g by the amount of substance ratio of Li:Ti:V:P=1:0.02:0.98:1, analyze pure grade titanium dioxide 1.597g, analyze pure level ammonium metavanadate 11.464g, analyze pure level ammonium di-hydrogen phosphate 11.503g, after mixing, add in nylon ball grinder, add again 60mL absolute ethyl alcohol, after sealing on planetary ball mill taking zirconia ball as ball-milling medium ball milling 4 hours, obtain rheology state jelly, 80 DEG C of dry 2h, grind to form fine powder, in argon gas atmosphere (0.5 liter/min), count 8h in 600 DEG C of sintering again, obtaining nominal composition formula is LiTi 0.02v 0.98oPO 4positive electrode powder.
The chemical property of gained sample is measured as follows: the sample that is 80% by mass fraction, 10% acetylene black and 10% Kynoar (PVDF), and be dissolved in solvent n-in methyl pyrrolidone (NMP), form slurry, slurry is evenly coated on aluminium foil, the thickness of coating is about 100 μ m.It is 1cm that the electrode slice coating is cut into area 2work electrode.At 60 DEG C, vacuumize 12h is for subsequent use.Test battery adopts conventional button cell, taking metallic lithium foil as to electrode, and 1.0 molL -1liPF 6ethyl carbonate EC/ dimethyl carbonate (DMC) (volume ratio is 1:1) solution be electrolyte, in the glove box that is full of argon gas, be assembled, digestion time is 6h.By 16mA/g(in positive pole) speed charge to 4.3V, be discharged to 3.0V, discharge curve obtains the stable discharge voltage plateau of 3.81V first, reversible specific capacity is about 154mAh/g first.After 30 circulations, specific discharge capacity is greater than 140 mAh/g.
 
embodiment 2
Take and analyze pure level lithium carbonate 7.389g by the amount of substance ratio of Li:Ti:V:P=1:0.04:0.96:1, analyze pure grade titanium dioxide 3.195g, analyze pure level ammonium metavanadate 11.23g, analyze pure level ammonium di-hydrogen phosphate 11.503g, after mixing, add in corundum ball grinder, add again 60mL acetone, after sealing on planetary ball mill taking agate ball as ball-milling medium ball milling 6 hours, obtain rheology state jelly, 80 DEG C of dry 2h, grind to form fine powder, in argon gas atmosphere (1.0 liters/min), count 8h in 600 DEG C of sintering again, obtaining nominal composition formula is LiTi 0.04v 0.96oPO 4positive electrode powder.
The chemical property of gained sample is measured as follows: the sample that is 80% by mass fraction, 10% acetylene black and 10% Kynoar (PVDF), and make electrode slice and be assembled into battery by embodiment 1.By 16mA/g(in positive pole) speed charge to 4.3V, be discharged to 3.0V, discharge curve obtains the stable discharge voltage plateau of 3.80V first, reversible specific capacity is about 153mAh/g first.After 30 circulations, specific discharge capacity is greater than 140 mAh/g.
embodiment 3
Take and analyze pure level lithium carbonate 7.389g by the amount of substance ratio of Li:Ti:V:P=1:0.06:0.94:1, analyze pure grade titanium dioxide 4.792g, analyze pure level ammonium metavanadate 10.996g, analyze pure level ammonium di-hydrogen phosphate 11.503g, after mixing, add in corundum ball grinder, add again 60mL deionized water, after sealing on planetary ball mill taking stainless steel ball as ball-milling medium ball milling 8 hours, obtain rheology state jelly, 80 DEG C of dry 2h, grind to form fine powder, in argon gas atmosphere (1.0 liters/min), count 10h in 600 DEG C of sintering again, obtaining nominal composition formula is LiTi 0.06v 0.94oPO 4positive electrode powder.
The chemical property of gained sample is measured as follows: the sample that is 80% by mass fraction, 10% acetylene black and 10% Kynoar (PVDF), and make electrode slice and be assembled into battery by embodiment 1.By 16mA/g(in positive pole) speed charge to 4.3V, be discharged to 3.0V, discharge curve obtains the stable discharge voltage plateau of 3.81V first, reversible specific capacity is about 149mAh/g first.After 30 circulations, specific discharge capacity is greater than 140 mAh/g.

Claims (10)

1. the titanium doped vanadyl phosphate lithium anode material of lithium ion battery, is characterized in that: its nominal composition formula is LiTi xv 1-xoPO 4, wherein, doping scope 0 < x < 0. 1.
2. prepare the method for the titanium doped vanadyl phosphate lithium anode material of lithium ion battery claimed in claim 1 for one kind, it is characterized in that being combined to mode by the rheology after parent stock and titanium source mixing and ball milling: lithium source, titanium source, He Lin source, vanadium source is by Li:Ti:V:P=1:x:(1-x): the amount of substance of 1 (0 < x < 0.1) adds the container of mixing and ball milling than raw materials weighing, then add ball-milling medium and dispersant ball milling, mixing and ball milling time 4-6 hour, obtain rheology state jelly, 60-80 DEG C of dry 2h, grind to form fine powder, in certain atmosphere, count 6-10h in 400 DEG C of-800 DEG C of sintering again, obtain the titanium doped vanadyl phosphate powder for lithium of nominal composition formula.
3. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: dispersant is one or more the mixture in deionized water, industrial alcohol, absolute ethyl alcohol, acetone.
4. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: the container of mixing and ball milling is the one in corundum ball grinder, agate jar, polyurethane ball-milling pot, nylon ball grinder, tungsten-carbide ball grinding jar.
5. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: ball-milling medium is the one in zirconia ball, corundum ball, agate ball, stainless steel ball, polyurethane ball.
6. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: lithium source is the one in lithium carbonate, lithium oxalate, lithium acetate, lithium hydroxide.
7. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: vanadium source is the one of vanadic oxide, ammonium metavanadate.
8. the preparation method of the titanium doped type vanadyl phosphate of lithium ion battery according to claim 2 lithium anode material, is characterized in that: phosphorus source is the one in diammonium hydrogen phosphate, ammonium dihydrogen phosphate.
9. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: titanium source is the one in titanium dioxide, butyl titanate, titanium sulfate or organic titanium salt.
10. the preparation method of the titanium doped vanadyl phosphate lithium anode material of lithium ion battery according to claim 2, is characterized in that: protective atmosphere is the one in nitrogen, argon gas, and protective atmosphere air-flow velocity is 0.1-8.0 liter/min.
CN201310068456.7A 2013-03-05 2013-03-05 Preparation method for titanium-doped lithium vanadyl phosphate positive electrode material used for lithium ion battery Pending CN104037409A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587063A (en) * 2016-12-19 2017-04-26 北方民族大学 Method for synthesizing titanium carbide through soft mechanical force chemical auxiliary microwaves
CN109817968A (en) * 2017-11-21 2019-05-28 宁德时代新能源科技股份有限公司 Surface-coated lithium nickel manganese oxide particles and method for producing same
CN112290019A (en) * 2020-10-21 2021-01-29 宁波大学 Fe3+、Ti4+Co-doped epsilon-LiVOPO4Lithium fast ion conductor and preparation method thereof
CN112390242A (en) * 2020-11-23 2021-02-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of titanium-doped lithium vanadium phosphate cathode material
CN116120050A (en) * 2023-02-15 2023-05-16 中国振华集团云科电子有限公司 Ultralow-temperature sintered LTCC ceramic material and preparation method thereof

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106587063A (en) * 2016-12-19 2017-04-26 北方民族大学 Method for synthesizing titanium carbide through soft mechanical force chemical auxiliary microwaves
CN109817968A (en) * 2017-11-21 2019-05-28 宁德时代新能源科技股份有限公司 Surface-coated lithium nickel manganese oxide particles and method for producing same
CN112290019A (en) * 2020-10-21 2021-01-29 宁波大学 Fe3+、Ti4+Co-doped epsilon-LiVOPO4Lithium fast ion conductor and preparation method thereof
CN112390242A (en) * 2020-11-23 2021-02-23 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of titanium-doped lithium vanadium phosphate cathode material
CN116120050A (en) * 2023-02-15 2023-05-16 中国振华集团云科电子有限公司 Ultralow-temperature sintered LTCC ceramic material and preparation method thereof
CN116120050B (en) * 2023-02-15 2023-12-19 中国振华集团云科电子有限公司 Ultralow-temperature sintered LTCC ceramic material and preparation method thereof

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Application publication date: 20140910