CN105406038A - High-capacity and high-cycle nanoscale lithium ferric manganese phosphate material synthesized by sol-gel method - Google Patents

High-capacity and high-cycle nanoscale lithium ferric manganese phosphate material synthesized by sol-gel method Download PDF

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Publication number
CN105406038A
CN105406038A CN201510732933.4A CN201510732933A CN105406038A CN 105406038 A CN105406038 A CN 105406038A CN 201510732933 A CN201510732933 A CN 201510732933A CN 105406038 A CN105406038 A CN 105406038A
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lithium
sol
source
manganese
manganese phosphate
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关成善
宗继月
孟博
薛娟娟
杜显振
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Shandong Goldencell Electronics Technology Co Ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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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Abstract

The invention relates to a high-capacity and high-cycle nanoscale lithium ferric manganese phosphate material synthesized by a sol-gel method and belongs to the technical field of lithium-ion batteries. A chemical formula of a cathode material lithium ferric manganese phosphate is LiFe<x>Mn<1-x>PO<4>, wherein x is smaller than 1 and greater than 0. The preparation method comprises the following steps: (1) firstly, weighing a lithium source, an iron source, a manganese source and a phosphorus source at a molar ratio, adding a carbon source and a solvent, and stirring the mixture into a sol state under a water bath condition; (2) standing the sol into a gel state; (3) drying the sol in a drying oven; (4) putting the sol into a tube furnace, sintering the sol in an inert gas atmosphere, pre-sintering the sol for 3-5 hours, cooling the sol to room temperature along with the furnace, rapidly grinding and crushing the sol, adding the product to the tube furnace, grading and sintering the product in the inert atmosphere, and carrying out air cooling to room temperature, so as to obtain the carbon-coated lithium ferric manganese phosphate cathode material.

Description

A kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material
Technical field
The invention belongs to cell positive material field in Material Field, particularly relate to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material.
Background technology
In recent years, containing Li phosphate LiMP0 4(M=Mn, Fe, Co, Ni etc.) are subject to whole world extensive concern as the research of lithium battery material, and element M is different, and charging/discharging voltage and the conductivity of its material also differ widely.Due to LiFeP0 4discharge voltage is lower, conductivity is relatively high and electrolyte is easily bought, so research comparison system, is also be studied one of maximum positive electrode at present.By contrast, due to LiMnP0 4conductivity is too poor, and being substantially identified as does not have electro-chemical activity, so people are to LiMnP0 4research be also nowhere near.But in fact with regard to material electrochemical performance, LiMnP0 4material compares LiFeP0 4have certain energy density advantage, and it is lower to the ingredient requirement of synthesis, synthesis condition is not high, Stability Analysis of Structures, so, LiMnP0 4cause people more and more to pay attention to.
Transition metal phosphate compound (LiFePO 4, LiMnPO 4) have good stability, toxicity low, pollute the advantages such as little, cheap, be current lithium ion battery LiCoO 2the important substitution material of positive pole.LiFePO 4lower voltage platform imply that lower energy density, which has limited its application in high-specific energy battery field.LiMnPO 4operating voltage be 4.1V, its theoretical energy density is LiFePO 4(operating voltage is 3.45V) 1.2 times.But due to too low lithium ion diffusion rate and native electronic conductance, LiMnPO 4often show poor chemical property.LiFe xmn 1-xpO 4positive electrode is exactly based on LiMnPO 4and LiFePO 4novel anode material between the two, and LiFePO 4compare, the charge and discharge potential part of this positive electrode can be brought up to 4.1V (vs.Li) by the introducing of Mn element, thus can improve the energy density of positive electrode to a great extent.And by reasonably adjusting ferrimanganic ratio, and coated by carbon, the modified methods such as metal ion mixing, reduce Jahn-Teller effect, improve electronic conductivity and the ion transportation of material, thus obtain higher chemical property.
This patent adopts sol-gal process to synthesize a kind of nanoscale iron phosphate manganese lithium material, more than 150mAh/g can be reached under specific discharge capacity 0.2C, can 145mAh/g be reached under 1C, circulate within 900 weeks, can keep 90% capability retention, be the positive electrode that a kind of chemical property is good.
Summary of the invention
The object of the invention is lithium ferric manganese phosphate as anode material for lithium-ion batteries, improve the problem of manganese-lithium phosphate anode material electron conduction difference, solve due to the structural instability problem that manganese element Jahn-Teller effect causes in lithium manganese phosphate simultaneously, improve specific discharge capacity and cycle performance.
The technical scheme that technical solution problem of the present invention adopts is as follows:
A kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material, is characterized in that: a kind of its chemical formula of positive pole material phosphoric acid ferrimanganic lithium is LiFe xmn 1-xpO 4, 0<x<1, is prepared by following methods:
(1) 1.0 ~ 1.2:(0.2 ~ 0.5 first in molar ratio): (0.5 ~ 0.8): 1.4 take a certain amount of lithium source, source of iron, manganese source, phosphorus source, then the carbon source of mass fraction 3% ~ 15% is added, add a certain amount of solvent, under 30 ~ 100 DEG C of water bath condition, electric mixer is utilized to be stirred to collosol state;
(2) by static for colloidal sol 5 ~ 24h, until gel state;
(3) dry in 80 DEG C ~ 120 DEG C drying boxes;
(4) put into tube furnace, sinter under atmosphere of inert gases, first pre-burning 3 ~ 5 hours under 240 ~ 390 DEG C of conditions.Cool to room temperature with the furnace, then material is ground fragmentation fast, then add in tube furnace, equally under an inert atmosphere classification sintering, sintering process is one-level 450 DEG C, 3 ~ 6 hours and secondary 780 DEG C, 5 ~ 24 hours; Control heating rate at 2 ~ 10 DEG C/min, air cooling, to room temperature, obtains the lithium ferric manganese phosphate positive electrode that carbon is coated.
Further, the mol ratio in described lithium source, source of iron, manganese source, phosphorus source is chosen as 1.0 ~ 1.2:0.2 ~ 0.5:0.5 ~ 0.8:1.4.
Further, the mol ratio in described lithium source, source of iron, manganese source, phosphorus source is chosen as 1.0 ~ 1.2:1:1:1.4.
Described lithium source is one or more in lithium nitrate, lithium acetate, lithium formate, lithium hydroxide, lithium carbonate, lithium chloride and lithium fluoride.
Described source of iron is one or more in ferric nitrate, ferrous oxalate and iron chloride.
Described phosphorus source is one or more in ferric phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
Described carbon source is one or more in citric acid, ascorbic acid, starch, farina, sucrose and glucose.
Described manganese source is one or more in acetic acid sub-manganese, manganese carbonate, acid manganous phosphate, manganese phosphate and manganese oxalate.
Described inert gas is nitrogen or argon gas.
Advantage of the present invention is: the lithium ferric manganese phosphate positive electrode obtained with sol-gal process is nano-scale particle, there is higher discharge voltage plateau (3.5V and 4.1V two platforms) and specific discharge capacity (can reach 145mAh/g under 1C, circulate within 900 weeks, can keep 90% capability retention), also there is the electron conduction (10 being better than lithium manganese phosphate -3~ 10 -4s/cm), this material preparation method is simple to operate simultaneously, environmentally safe.
Accompanying drawing explanation
Fig. 1 is LiFe prepared by the embodiment of the present invention 1 0.5mn 0.5pO 4scanning electron microscopic picture;
Fig. 2 is LiFe prepared by the embodiment of the present invention 1 0.5mn 0.5pO 40.2C charge-discharge property curve;
Fig. 3 is LiFe prepared by the embodiment of the present invention 1 0.5mn 0.5pO 41C cycle performance curve.
Embodiment
embodiment 1
First in molar ratio 1 ~ 1.2:1:1:1.4 takes a certain amount of lithium hydroxide, ferrous nitrate, acetic acid sub-manganese, phosphoric acid, add the glucose of 6% of slaine mass fraction and the citric acid of 2%, adding distilled water just makes it dissolve, ultrasonic disperse, then by solution under 60 DEG C of water bath condition electric stirring to collosol state, then static 15h is in gel state, then dry in 80 DEG C of drying boxes.Then put into tube furnace, sinter under atmosphere of inert gases, first pre-burning 3 hours under 360 DEG C of conditions.Put into tube furnace, sinter under atmosphere of inert gases, first pre-burning 3 ~ 5 hours under 240 ~ 390 DEG C of conditions.Then 450 DEG C, 2 hours, then 780 DEG C, 6 hours sintering; Control heating rate at 2 ~ 10 DEG C/min, air cooling, to room temperature, obtains the lithium ferric manganese phosphate positive electrode LiFe that carbon is coated 0.5mn 0.5pO 4.
With the lithium manganese phosphate of preparation for anode material for lithium-ion batteries, acetylene black is conductive agent, and Kynoar, makes electrode slice, take lithium metal as negative pole, composition button cell.Test under the discharge and recharge condition of 0.2C, test result is shown in accompanying drawing 1.As can be seen from the figure, the first discharge specific capacity of this material is 152mAh/g, and efficiency for charge-discharge is 99.7%; Fig. 2 is this material 1C cycle performance curve, and 1C circulates after 900 times, and capability retention is 90%.
embodiment 2
First in molar ratio 1 ~ 1.2:1:1:1.4 takes a certain amount of lithium acetate, frerrous chloride, acetic acid sub-manganese, phosphoric acid, add the citric acid of 8% of slaine mass fraction, add and the absolute ethyl alcohol taking all raw material volume 3 times, then by solution under 30 DEG C of water bath condition electric stirring to collosol state, then static 5h, in gel state, then dry in 80 DEG C of drying boxes.Then put into tube furnace, sinter under atmosphere of inert gases, first pre-burning 3 hours under 300 DEG C of conditions.With putting into tube furnace, sinter under atmosphere of inert gases, first pre-burning 3 ~ 5 hours under 240 ~ 390 DEG C of conditions.Then 550 DEG C, 2 hours, then 680 DEG C, 10 hours sintering; Control heating rate at 2 ~ 10 DEG C/min, air cooling, to room temperature, obtains the lithium ferric manganese phosphate positive electrode LiFe that carbon is coated 0.5mn 0.5pO 4.
Above-described embodiment has been described in detail technical scheme of the present invention; be understood that and the foregoing is only specific embodiments of the invention; be not limited to the present invention; all any amendments and improvement etc. made in spirit of the present invention, all should be included within protection scope of the present invention.

Claims (9)

1. a sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material, is characterized in that: a kind of its chemical formula of positive pole material phosphoric acid ferrimanganic lithium is LiFe xmn 1-xpO 4, 0<x<1, a kind of sol-gal process synthesis high power capacity height circulation classification sintering nanoscale iron phosphate manganese lithium material is prepared by following methods:
(1) 1.0 ~ 1.2:x:1-x:1.4 first in molar ratio, 0<x<1, take a certain amount of lithium source, source of iron, manganese source, phosphorus source, then the carbon source of mass fraction 3% ~ 15% is added, add a certain amount of solvent, under 30 ~ 100 DEG C of water bath condition, electric mixer is utilized to be stirred to collosol state;
(2) colloidal sol is left standstill 5 ~ 24h, until gel state;
(3) dry in 80 DEG C ~ 120 DEG C drying boxes;
(4) tube furnace is put into, sinter under atmosphere of inert gases, first pre-burning 3 ~ 5 hours under 240 ~ 390 DEG C of conditions, cool to room temperature with the furnace, then material is ground fragmentation fast, then add in tube furnace, classification sintering equally under an inert atmosphere, sintering process is one-level 450 DEG C, 3 ~ 6 hours and secondary 780 DEG C, 5 ~ 24 hours; Control heating rate at 2 ~ 10 DEG C/min, air cooling, to room temperature, obtains the lithium ferric manganese phosphate positive electrode that carbon is coated.
2., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described in preparation process (1) lithium source, source of iron, manganese source, phosphorus source mol ratio be chosen as 1.0 ~ 1.2:0.2 ~ 0.5:0.5 ~ 0.8:1.4.
3. according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 2, it is characterized in that: the mol ratio in described lithium source, source of iron, manganese source, phosphorus source is chosen as 1.0 ~ 1.2:1:1:1.4.
4., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described lithium source is one or more in lithium nitrate, lithium acetate, lithium formate, lithium hydroxide, lithium carbonate, lithium chloride and lithium fluoride.
5., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described source of iron is one or more in ferric nitrate, ferrous oxalate and iron chloride.
6., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described phosphorus source is one or more in ferric phosphate, ammonium dihydrogen phosphate, diammonium hydrogen phosphate and phosphoric acid.
7., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described carbon source is one or more in citric acid, ascorbic acid, starch, farina, sucrose and glucose.
8., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described manganese source is one or more in acetic acid sub-manganese, manganese carbonate, acid manganous phosphate, manganese phosphate and manganese oxalate.
9., according to a kind of sol-gal process synthesis high power capacity height circular nanometer level lithium ferric manganese phosphate material described in claim 1, it is characterized in that: described inert gas is nitrogen or argon gas.
CN201510732933.4A 2015-11-03 2015-11-03 High-capacity and high-cycle nanoscale lithium ferric manganese phosphate material synthesized by sol-gel method Pending CN105406038A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711411A (en) * 2016-12-07 2017-05-24 深圳市沃特玛电池有限公司 Preparation method of lithium iron phosphate/carbon composite material
CN106920950A (en) * 2017-04-25 2017-07-04 上海电力学院 A kind of preparation method of high circulation, powerful carbon based negative electrodes energy-storage composite material
CN108511724A (en) * 2018-04-04 2018-09-07 广州大学 A kind of collosol and gel auxiliary supercritical CO2Drying prepares iron manganese phosphate for lithium method
CN111224103A (en) * 2020-01-17 2020-06-02 贝特瑞（天津）纳米材料制造有限公司 Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material
CN114204021A (en) * 2021-11-05 2022-03-18 四川龙蟒磷化工有限公司 Preparation method of low-cost lithium iron manganese phosphate
CN115332516A (en) * 2022-08-29 2022-11-11 重庆长安新能源汽车科技有限公司 Magnesium and nickel co-doped lithium manganese iron phosphate cathode material and preparation method thereof
CN116281932A (en) * 2023-04-18 2023-06-23 上海量孚新能源科技有限公司 Lithium iron manganese phosphate and preparation method and application thereof

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* Cited by examiner, † Cited by third party
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CN101645504A (en) * 2008-08-07 2010-02-10 赵兵 Method for preparing lithium iron phosphate of anode material of lithium ion battery
CN102299317A (en) * 2011-07-14 2011-12-28 上海微纳科技有限公司 High-rate LiFePO4/mesoporous carbon composite cathode material and preparation method thereof
WO2012085150A2 (en) * 2010-12-22 2012-06-28 Süd-Chemie AG Titano-silico-alumo-phosphate
CN103985871A (en) * 2014-05-27 2014-08-13 宁波艾能锂电材料科技股份有限公司 Preparation method for positive electrode material of iron, lithium and manganese phosphate battery
CN104409688A (en) * 2014-10-29 2015-03-11 中航锂电（洛阳）有限公司 Lithium iron phosphate material for lithium ion power battery, and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101645504A (en) * 2008-08-07 2010-02-10 赵兵 Method for preparing lithium iron phosphate of anode material of lithium ion battery
WO2012085150A2 (en) * 2010-12-22 2012-06-28 Süd-Chemie AG Titano-silico-alumo-phosphate
CN102299317A (en) * 2011-07-14 2011-12-28 上海微纳科技有限公司 High-rate LiFePO4/mesoporous carbon composite cathode material and preparation method thereof
CN103985871A (en) * 2014-05-27 2014-08-13 宁波艾能锂电材料科技股份有限公司 Preparation method for positive electrode material of iron, lithium and manganese phosphate battery
CN104409688A (en) * 2014-10-29 2015-03-11 中航锂电（洛阳）有限公司 Lithium iron phosphate material for lithium ion power battery, and preparation method thereof

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106711411A (en) * 2016-12-07 2017-05-24 深圳市沃特玛电池有限公司 Preparation method of lithium iron phosphate/carbon composite material
CN106920950A (en) * 2017-04-25 2017-07-04 上海电力学院 A kind of preparation method of high circulation, powerful carbon based negative electrodes energy-storage composite material
CN108511724A (en) * 2018-04-04 2018-09-07 广州大学 A kind of collosol and gel auxiliary supercritical CO2Drying prepares iron manganese phosphate for lithium method
CN111224103A (en) * 2020-01-17 2020-06-02 贝特瑞（天津）纳米材料制造有限公司 Preparation method of metal ion-doped high-rate mesoporous lithium iron phosphate cathode material
CN114204021A (en) * 2021-11-05 2022-03-18 四川龙蟒磷化工有限公司 Preparation method of low-cost lithium iron manganese phosphate
CN114204021B (en) * 2021-11-05 2024-01-26 四川龙蟒磷化工有限公司 Preparation method of low-cost lithium iron manganese phosphate
CN115332516A (en) * 2022-08-29 2022-11-11 重庆长安新能源汽车科技有限公司 Magnesium and nickel co-doped lithium manganese iron phosphate cathode material and preparation method thereof
CN116281932A (en) * 2023-04-18 2023-06-23 上海量孚新能源科技有限公司 Lithium iron manganese phosphate and preparation method and application thereof

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