CN102709554B - LiMnPO4/C composite cathode material preparation method for lithium ion battery - Google Patents
LiMnPO4/C composite cathode material preparation method for lithium ion battery Download PDFInfo
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- CN102709554B CN102709554B CN201210174368.0A CN201210174368A CN102709554B CN 102709554 B CN102709554 B CN 102709554B CN 201210174368 A CN201210174368 A CN 201210174368A CN 102709554 B CN102709554 B CN 102709554B
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- lithium
- acetate
- limnpo4
- carbon
- lithium ion
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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 LiMnPO4/C composite cathode material preparation method for a lithium ion battery, and belongs to the technical field of lithium ion batteries. Lithium acetate, manganese acetate and ammonium dihydrogen phosphate are taken as raw materials, an oxalic acid is taken as a precipitating agent, and sucrose is taken as a carbon source. The method comprises the following steps of: preparing a precipitation precursor, and performing calcinations to prepare a micro-nano LiMnPO4/C composite cathode material with high electrical conductivity. The method is easy, feasible, energy-saving and time-saving; LiMnPO4 in the prepared material is high in purity and crystallinity; surface coating carbon can be obtained by a one-step method; and the proportion of the LiMnPO4 and the conductive carbon in the composite material is easily controlled, so that the performance optimization of the material is facilitated.
Description
Technical field
The present invention relates to adopt the lithium manganese phosphate/carbon (LiMnPO of precipitation transformation method for the preparation of lithium ion cell positive
4/ C) composite material, belong to technical field of lithium ion.
Background technology
Along with social progress and the fast development of electronic information technology, the miniaturization gradually of electronic instrument and communication equipment, therefore increases rapidly to the demand of portable power source, its performance is also had higher requirement simultaneously.In addition, the research and development of electric motor car in recent years and electrical source of power thereof and application also receive much concern.Lithium ion battery is the secondary cell of a class high-energy-density.At present, the capacity of anode material for lithium-ion batteries is lower than negative material, and therefore exploitation cheapness, environmental protection and high performance positive electrode are the Research Emphasis of lithium ion battery always.In anode material for lithium-ion batteries, the LiCoO of layer structure
2obtain business application.But the rare and fancy price of cobalt resource has limited its large-scale application.
The olivine-type LiMPO that can reversiblely discharge and recharge in recent years,
4(M=Fe, Mn, Ni, Co) anode material for lithium-ion batteries has caused people's concern.In this class material, that research and develop at present morely is LiFePO
4material, is regarded as the safer power lithium-ion battery positive electrode of electric vehicle.With LiFePO
4electrode is compared, LiMnPO
4the theoretical capacity of electrode and LiFePO
4quite, but its work potential (4.1 V vs. Li
+/ Li) but apparently higher than LiFePO
4electrode (3.4 V vs. Li
+/ Li).Therefore, with LiMnPO
4there is potential higher energy density and power density as anodal lithium ion battery.In addition LiMnPO,
4also having advantages of that cost is low and Environmental compatibility is good, is a kind of positive electrode with development prospect.But LiMnPO
4material has the poor and slow shortcoming of lithium ion diffusion velocity of electron conduction.In order to improve LiMnPO
4conductivity, can adopt material and the LiMnPO of good conductivity
4compound or at LiMnPO
4the coated one deck conductive carbon in surface of material, to improve its chemical property.
Compared with non-aqueous solution lithium ion battery, Water-soluble lithium ion battery has advantages of that fail safe is good, cost is low and electrolytic conductivity is high.2006, seminar's reported first of Australian Univ Murdoch LiMnPO
4the chemical property of electrode in the saturated LiOH aqueous solution.The initial discharge capacity of this electrode is about 75 mAh/g, and after 10 charge and discharge cycles, capacity is reduced to 38 mAh/g.The present invention adopts precipitation transformation method to prepare LiMnPO
4/ C composite material, this composite material is at 2 mol/L Li
2sO
4charge and discharge cycles stability in neutral aqueous solution electrolyte is obviously better than above-mentioned material.
Summary of the invention
The object of the invention is to adopt a kind of new method, i.e. the synthetic a kind of new type lithium ion battery anode composite material LiMnPO of precipitation transformation method
4/ C, the method preparation technology is easy, with low cost.
A kind of lithium ion cell positive LiMnPO of the present invention
4the preparation method of/C composite material, is characterized in that having following preparation process and step:
A. oxalic acid and lithium acetate are dissolved in deionized water by the mol ratio of 2:1, add appropriate sucrose, magnetic agitation mixes it; The silly addition of sugarcane is 80～86wt% of lithium acetate quality;
B. will be dissolved in respectively in a certain amount of deionized water with manganese acetate and the phosphoric acid dihydro amine of lithium acetate equimolar ratio, under magnetic agitation, manganese acetate solution is added drop-wise in the mixed solution of oxalic acid, lithium salts and sucrose with the speed of 1 drop/sec, obtains pink precipitation, then drip biphosphate amine aqueous solution; Lithium acetate, manganese acetate and phosphoric acid dihydro amine three's mol ratio is 1:1:1;
C. by above-mentioned system transpiring moisture in 70 DEG C of water-baths, then in vacuum drying chamber in 120 DEG C dry, grind into powder, obtains precursor.Precursor is slowly warmed up to 650 DEG C with the programming rate of 2 DEG C/min under blanket of nitrogen, and at 650 DEG C, calcines 12 h, obtain black lithium manganese phosphate/carbon (LiMnPO of coated with carbon
4/ C) composite material.
The present invention has the following advantages:
1, prepare LiMnPO with precipitation transformation method
4the technical process of/C composite material is simple, pollution-free, and LiMnPO in composite material
4be easy to control with the ratio of C.Wherein use oxalic acid as precipitation reagent, oxalic acid generates reducibility gas after high-temperature calcination, can stop the oxidation of divalent manganesetion, and oxalic acid is all converted into gas afterwards in calcining, does not affect the stoichiometry of phosphorus content.
2, in the preparation process of material, the compound of carbon obtains by one-step method, without first preparing LiMnPO
4material carries out charing processing again, therefore saves time and energy.And before precipitation forms, carbon source is just evenly mixed with reactant, so after precipitation formation, carbon source material is evenly distributed in sedimentary surface, after heat treatment, obtains the LiMnPO of good conductivity
4/ C composite material.
3, carbon is compound can effectively improve LiMnPO
4the conductivity of material, thus its chemical property improved, as electro-chemical activity and cyclical stability.
4, the LiMnPO preparing
4/ C composite material is nano-micro structure material, is suitable as the positive electrode of lithium ion battery.The too small meeting of active material particle causes material capacity attenuation in cyclic process fast, and the excessive diffusion that is unfavorable for lithium ion of particle, affects chemical property.
Brief description of the drawings
Fig. 1 is the LiMnPO being prepared by embodiment 1
4the XRD figure of/C composite material.
Fig. 2 is the LiMnPO being prepared by embodiment 1
4the TEM figure of/C composite material.
Fig. 3 is the LiMnPO being prepared by embodiment 1
4the cycle performance of/C composite electrode.
Embodiment
embodiment 1
The preparation method of manganese phosphate lithium/carbon composite material for the present embodiment lithium ion cell positive, comprises the following steps:
(1) take 0.04mol oxalic acid, 0.02mol lithium acetate crystal is placed in the clean beaker of a 500mL, measures 60ml deionized water and is dissolved, and magnetic agitation mixes, then adds 1.7444g sucrose, and magnetic agitation 30min, is referred to as mixed solution A.
(2) take 0.02mol manganese acetate crystal and be placed in the clean beaker of a 50mL, measure 30mL deionized water and dissolved, magnetic agitation is even, is made into the manganese acetate solution of 0.67mol/L.The manganese acetate solution preparing is added drop-wise in mixed solution A with the speed of 1 drop/sec with plastic dropper, and carries out powerful magnetic agitation during the course, form the mixture of pink precipitation and solution, be referred to as mixture B.Get 0.02mol phosphoric acid dihydro amine crystal and be placed in former 50ml beaker, measure 30mL deionized water and dissolved, magnetic agitation is even, is made into 0.67mol/L's
Biphosphate ammonia solution, is added drop-wise to this solution in mixture B with speed slowly, and magnetic agitation is even, still the mixture of pink precipitation and solution, be referred to as mixture C.Get again 20mL deionization moisture several times and clean after 50mL beaker, pour in mixture, stir.
(3), by said mixture system transpiring moisture in 70 DEG C of water-baths, constantly magnetic agitation, until the pink spawn that obtains being dried.This substance transfer, to the surface plate of dried and clean, is evenly spread out, be placed in vacuum drying chamber (vacuum degree is-0.07MPa) after 120 DEG C of dry 12h, close drying box and keep vacuum state naturally to lower the temperature, after cool to room temperature, fully grind, obtain presoma.Presoma is placed in to tube furnace, in nitrogen protection atmosphere, is slowly warmed up to 650 DEG C with the programming rate of 2 DEG C/min; and at 650 DEG C, calcine 12 h; still in nitrogen protection atmosphere, be down to room temperature, obtain target product, be i.e. black lithium manganese phosphate/carbon (LiMnPO of coated with carbon
4/ C) composite material.
liMnPO
4
the cycle performance test of/C composite electrode material
Charge-discharge test adopts three-electrode system:
Work electrode preparation: lithium manganese phosphate-carbon composite: acetylene black: PTFE=75%/20%/5%(mass ratio), after mixing and stirring, blade coating is in clean titanium mesh grid, and in vacuum drying chamber, dry 12h at 105 DEG C, is flattened into experience thickness through roll squeezer.
Auxiliary electrode preparation: active carbon: acetylene black: PTFE=80%/10%/10%(mass ratio), after mixing and stirring, blade coating is on clean nickel screen, and in vacuum drying chamber, dry 12h at 105 DEG C, is flattened into experience thickness through roll squeezer.
Reference electrode is saturated calomel electrode (SCE), and electrolyte is for using deionized water and Li
2sO
4h
2o white crystalline powder configures the 2M Li forming
2sO
4solution, the voltage range discharging and recharging is 0 ~ 1.1V
vs. SCE.The measurement that discharges and recharges the life-span is used LAND battery performance test instrument, and charge-discharge magnification is 0.1C.
Every instrument testing result of the present embodiment products therefrom is shown in following accompanying drawing.
Fig. 1 is LiMnPO
4x-ray diffraction (XRD) spectrogram of/C material.As seen from the figure, all diffraction maximums all and LiMnPO
4standard spectrogram (PDF no. 33-0804) match, show the LiMnPO in this material
4for the LiMnPO of mutually pure olivine-type structure
4(rhombic system, space group is Pmnb), and there is good degree of crystallinity.
Fig. 2 is LiMnPO
4transmission electron microscope (TEM) photo of/C material.As seen from the figure, this material is made up of the particle that is of a size of hundreds of nanometer, belongs to nano-micro structure material.
Fig. 3 is LiMnPO
4/ C electrode is at 2 mol/L Li
2sO
4charge-discharge performance in neutral aqueous solution electrolyte.As seen from the figure, except the discharge capacity of the 2nd circulation declines to some extent, totally more steady.Cyclical stability is better than the situation of bibliographical information
[1].Due to LiMnPO
4/ C is unstable in the aqueous solution, and has the existence of analysing oxygen side reaction, has limited the performance of its capacity, and the research of domestic this respect is at present also in blank.Bibliographical information LiMnPO before
4/ C is very unstable in the saturated LiOH aqueous solution, and front ten times discharge capacity decays to 50%.Consider and in alkaline solution, be easy to analyse oxygen side reaction on the one hand, this patent adopts 2 mol/L Li first
2sO
4neutral electrolyte, has suppressed the generation of side reaction to a certain extent, and the efficiency that main reaction occurs is guaranteed; The particle of preparation is the coated intact nano-micro structure of carbon on the other hand, reduce with aqueous solution contact area in, brought into play its maximum chemical property.These 2 cause the specific discharge capacity shown in this figure and cycle performance to be all better than previous bibliographical information.
list of references:
M.?Minakshi,?P.?Singh,?S.?Thurgate,?K.?Prince,?Electrochem.?Solid-State?Lett.?9?(2006)?A471。
Claims (1)
1. a preparation method for manganese phosphate lithium/carbon composite material for lithium ion cell positive, is characterized in that having following preparation process and step:
A. oxalic acid and lithium acetate are dissolved in deionized water by the mol ratio of 2:1, add appropriate sucrose, magnetic agitation mixes it; The addition of sucrose is 80～86wt% of lithium acetate quality;
B. will be dissolved in respectively in a certain amount of deionized water with manganese acetate and the phosphoric acid dihydro amine of lithium acetate equimolar ratio, under magnetic agitation, manganese acetate solution is added drop-wise in the mixed solution of oxalic acid, lithium salts and sucrose with the speed of 1 drop/sec, obtains pink precipitation, then drip biphosphate amine aqueous solution; Lithium acetate, manganese acetate and phosphoric acid dihydro amine three's mol ratio is 1:1:1;
C. by above-mentioned system transpiring moisture in 70 DEG C of water-baths, then in vacuum drying chamber in 120 DEG C dry, grind into powder, obtains precursor; Precursor is slowly warmed up to 650 DEG C with the programming rate of 2 DEG C/min under blanket of nitrogen, and at 650 DEG C, calcines 12 h, obtain black lithium manganese phosphate/carbon (LiMnPO of coated with carbon
4/ C) composite material.
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| CN105226272A (en) * | 2014-05-27 | 2016-01-06 | 中国科学院苏州纳米技术与纳米仿生研究所 | Lithium manganese phosphate-carbon composite and preparation method thereof, positive electrode and positive pole |
| CN111389432B (en) * | 2020-04-28 | 2021-07-06 | 中国科学技术大学 | Carbon-coated bimetallic olivine-phase cobalt manganese lithium phosphate material, and preparation method and application thereof |
| CN113224278B (en) * | 2021-05-07 | 2022-06-07 | 蜂巢能源科技有限公司 | Modified lithium ferric manganese phosphate material, preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102074686A (en) * | 2010-12-16 | 2011-05-25 | 广州市香港科大***研究院 | Method for synthesizing manganese lithium phosphate/carbon serving as positive material of lithium ion battery |
| CN102280621A (en) * | 2011-07-06 | 2011-12-14 | 大连理工大学 | Method for preparing lithium ion battery material lithium and manganese phosphate/carbon by adopting sol-gel method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102074686A (en) * | 2010-12-16 | 2011-05-25 | 广州市香港科大***研究院 | Method for synthesizing manganese lithium phosphate/carbon serving as positive material of lithium ion battery |
| CN102280621A (en) * | 2011-07-06 | 2011-12-14 | 大连理工大学 | Method for preparing lithium ion battery material lithium and manganese phosphate/carbon by adopting sol-gel method |
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