CN101937987B - Method for preparing composite anode material LiFePO4/C for lithium ion battery - Google Patents
Method for preparing composite anode material LiFePO4/C for lithium ion battery Download PDFInfo
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- CN101937987B CN101937987B CN201010246621XA CN201010246621A CN101937987B CN 101937987 B CN101937987 B CN 101937987B CN 201010246621X A CN201010246621X A CN 201010246621XA CN 201010246621 A CN201010246621 A CN 201010246621A CN 101937987 B CN101937987 B CN 101937987B
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- lithium
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- lifepo
- lifepo4
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- 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 method for preparing a composite anode material LiFePO4/C for a lithium ion battery. The method comprises the steps of mixing, reacting, drying, calcining and cooling and is characterized in that: lithium salt, ferric salt and phosphate are mixed with a chemical substance, namely, formaldehyde capable of forming an ideal carbon gel pre-condensed substance and a resorcinol composition so as to form a complex rheological phase reaction system for preparing an LiFePO4/C high molecular polymer; and reaction substances for preparing the LiFePO4 are uniformly distributed in the carbon gel pre-condensed substance. Simultaneously, polyethylene glycol (PEG) is added, pH is controlled and a reaction system is adjusted so as to adjust the structure of the carbon gel pre-condensed substance, a netlike porous structural material which is distributed uniformly can be obtained by calcining and carbon is uniformly coated on the surface of the LiFePO4. Under the condition of10C multiplying power, discharge specific capacity is up to 120.56mAh/g and circulating performance is high. The prepared anode material has a stable structure and high cyclical stability, does not contain any heavy metal and is an environmentally-friendly material.
Description
One, technical field
The present invention relates to a kind of method for preparing anode material of lithium-ion battery, exactly is a kind of lithium ion battery composite cathode material LiFePO
4The preparation method of/C.
Two, background technology
The LiFePO of olivine structural
4Embedding that can be reversible and deviate from lithium ion is considered to one of alternative electrode material of lithium ion battery.Show that after deliberation this material has following advantage: raw material is cheap, does not contain heavy metal, aboundresources, environmental friendliness; Operating voltage moderate (3.4V), platform identity is good; Theoretical capacity is large, Stability Analysis of Structures, and security performance is good; High-temperature behavior and good cycle; To reach well storge quality good with most of electrolyte system compatibilities.
Preparation LiFePO
4Method mainly contain solid phase method, sol-gal process, microwave process for synthesizing, oxidation-reduction method and hydro thermal method etc.About LiFePO
4The research of solid-phase synthesis relatively early, but its synthetic method time is long, heat utilization ratio is low, particle is inhomogeneous and the impurity phase of iron occurs easily.LiFePO
4Microwave method and hydro thermal method because of shortcomings such as its output are little, be difficult to carry out suitability for industrialized production.And the sol-gal process advantage is that its precursor solution chemistry uniformity is fine, the Gel heat-treatment temperature is low, equipment is simple, the powder handling performance is good etc.
Different gel rubber systems is to preparation cell positive material LiFePO
4The structure of/C and performance be difference to some extent, the people (LiFePO such as Luo Shaohua
4The performance of/CNT composite positive pole [J], battery, 2009, (03) 151-152) by in preparation electrode material process, adds citric acid, consists of the organic complex reaction system, forms gel.The battery composite anode material material LiFePO of preparation
4/ CNT discharges and recharges at 0.2C, 1.0C and 2.0C, and its specific discharge capacity is respectively 135mAh/g, 110mAh/g and 80mAh/g.Simultaneously, some research work have launched the complexing agents such as adding tartaric acid, ascorbic acid, consist of the organic complex reaction system, make gel, and the drying calcination process makes LiFePO
4/ C positive electrode.(such as document S.B.Leea, I.C.Jang, H.H.Lima, et al.Preparation and electrochemical characterization of LiFePO4 nanoparticles with high rate capability by a sol-gel method[J], Journal of Alloys and Compounds, 491 (2010) 668-672 and patents: based on the process for preparing sol-gel of the lithium iron phosphate cathode material of ferric phosphate, application number: 200910069472.1 etc.).With Publication about Document: numb bright friend, anode material for lithium-ion batteries LiFePO
4The preparation of/C and sign [J], JOURNAL OF JISHOU UNIVERSITY (natural science edition), 2004, (03), 64-67; Patent: a kind of preparation method of high-density spherical ferric lithium phosphate, application number: 200510000167.9 grades have been reported and adopted surfactants such as adding Tween 85 and Span80 in preparation process, consist of the emulsion reaction system, form gel, the drying calcination process makes uniform particles or spherical structure LiFePO
4/ C positive electrode does not obtain equally distributed mesh structural porous structural material.Patent: lithium ferrous phosphate as anode material of lithium ion battery collosol-coating preparation method, application number: 200910069069.9 and patent: lithium ferrous phosphate as anode material of lithium ion battery collosol-coating preparation method, application number: 200910069069.9 have reported that employing adds starch, pass through starch gelatinization, consist of simple sol system, form gel, the drying calcination process makes LiFePO
4/ C positive electrode.Patent: the preparation method of active substance ferrous lithium phosphate as lithium-ion battery anode, application number: 200510132155.1, by the LiFePO in preparation
4Add the high molecular polymers such as phenolic resins in the presoma, consist of simple sol system, form gel, prepared LiFePO
4/ C material.But the positive electrode LiFePO of these method preparations
4There is even not, the large high not performance limitations of multiplying power discharging of particle in/C.
Three, summary of the invention
The present invention aims to provide a kind of lithium ion battery composite cathode material LiFePO
4/ C preparation method, technical problem to be solved evenly distribute lithium salts, molysite and phosphate in the charcoal gel, thereby the LiFePO of charcoal, function admirable is evenly covered in preparation
4/ C positive electrode.
Thinking of the present invention is to mix with the same lithium salts of phenol, molysite and phosphate with the pre-condensate formaldehyde that can form the charcoal gel to form colloidal sol, consists of preparation LiFePO
4/ C high molecular polymer rheology phase complex reaction system makes synthetic LiFePO
4Each reactive material in charcoal Gel Pre condensate, form evenly and distribute.By adding polyethylene glycol (PEG) and control pH value in the body in reaction, and then the structure of adjustment charcoal Gel Pre condensate, after calcination process, obtain equally distributed mesh structural porous structural material, and carbon evenly is coated on LiFePO
4The surface.Under the large multiplying power condition, first discharge specific capacity is high, and cycle performance is good.
This composite positive pole LiFePO
4The preparation method of/C, take lithium salts, molysite and phosphate as raw material, comprise each unit process of mixing, reaction, drying, ball milling, calcining and cooling, difference with the prior art be with lithium salts, molysite, phosphate, resorcinol and PEG in molar ratio 0.85～1.45: 0.95～1.60: 0.8～1.50: 1.5～2.8: 0.75～1.65 mix soluble in water, add at last formalin, the mol ratio of formaldehyde and resorcinol 2: 1, in 30～80 ℃ of lower stirrings and accent pH 3.5～10.5, simultaneously ultrasonic dispersion makes colloidal sol; Colloidal sol dehydrated obtain xerogel; With behind the xerogel ball milling in 300～450 ℃ of lower pre-burnings 5～10 hours, under reducing atmosphere, obtained composite positive pole LiFePO in 4～16 hours in 600～950 ℃ of calcinings at last
4/ C.The mesh structural porous structure that this material is evenly distributed, and carbon evenly is coated on LiFePO
4The surface.As shown in Figure 2.
Described pH value 3.5～10.5 is for transferring the acid of pH3.5～6.4 or transferring the alkalescence of pH7.5～10.5 or with the neutrality of hydrochloric acid, ammoniacal liquor accent pH6.5～7.4 with ammoniacal liquor with hydrochloric acid.
Described lithium salts is selected from lithium hydroxide, lithium chloride or lithium acetate;
Described molysite is selected from frerrous chloride, ferrous oxalate or ironic citrate;
Described phosphate is selected from lithium phosphate, ammonium phosphate or diammonium hydrogen phosphate;
Described reducing atmosphere is the gaseous mixture of hydrogen or carbon monoxide and argon gas or nitrogen.
Concrete operation step is described below:
1, with in molar ratio 0.85-1.45: 0.95-1.60: 0.8-1.50: 1.5-2.8,0.75-1.65 mixing of lithium salts, molysite, phosphate, resorcinol and PEG, is dissolved in water.Measure formalin, the mol ratio that makes formaldehyde and resorcinol is to add in mentioned solution at 2: 1.Constant temperature stirs, and regulates the pH value:
Catalytic reaction under the alkali condition, control pH=7.5-10.5 can adopt ammoniacal liquor to regulate;
Catalytic reaction under the acid condition, control pH=3.0-6.4 can adopt hydrochloric acid to regulate;
Catalytic reaction under the neutrallty condition scope, pH=6.5-7.4 can adopt the different proportion of hydrochloric acid and ammoniacal liquor to regulate.
2, the mixed solution that obtains in above-mentioned 1 step is stirred 2-6h at 30-80 ℃ of constant temperature, ultrasonic dispersion makes colloidal sol;
3, the colloidal sol that system in above-mentioned 2 steps is arrived, 80-180 ℃ of dry 0.5-36h sloughs aqueous solvent, obtains xerogel;
4, the xerogel that system in above-mentioned 3 steps is arrived, ball milling 4-18h on planetary ball mill, rotating speed are 600 rev/mins.Fully grind afterwards pre-burning 5-10h under 300-450 ℃ of temperature;
5, with the pre-burning product in above-mentioned 4 steps, 600-900 ℃ of calcination under protection of reducing atmosphere.Constant temperature 4-16h under calcination temperature.Cooling down can obtain powder LiFePO to room temperature
4/ C composite material.
The chemical substance formaldehyde and the resorcinol that the present invention is based on can form charcoal Gel Pre condensate make up, and consist of preparation LiFePO
4/ C high molecular polymer rheology phase complex reaction system will prepare the reactive material that generates LiFePO4 and form evenly distribution in charcoal Gel Pre condensate.Add PEG and control pH adjustment reaction system, and then adjust the structure of charcoal Gel Pre condensate, after calcination process, obtain equally distributed mesh structural porous structural material, and carbon evenly is coated on LiFePO
4The surface.Under the large multiplying power condition, first discharge specific capacity is high, and cycle performance is good.The invention provides a kind of LiFePO that evenly covers charcoal, function admirable for preparing
4The new method of/C positive electrode.This positive electrode has the stably charging/discharging voltage platform about 3.4V, and its electric conductivity and heavy-current discharge performance are good simultaneously.Reversible specific discharge capacity reaches 120.56mAh/g under the 10C multiplying power condition, and this composite structure is stable, and good cycling stability does not contain heavy metal, is the environmental friendliness shaped material.
Four, description of drawings
Fig. 1 is the XRD figure of this iron phosphate compound anode material of lithium;
Fig. 2 is the SEM figure of this iron phosphate compound anode material of lithium, and as can be seen from the figure, material is porous nanometer structure;
Fig. 3 is the charging and discharging curve figure of the battery of this iron phosphate compound anode material of lithium processing;
Fig. 4 is the high rate performance figure of the battery of this iron phosphate compound anode material of lithium processing.
Five, embodiment
Embodiment 1
1) takes by weighing 0.5mol lithium hydroxide, 0.65mol frerrous chloride, 0.70mol diammonium hydrogen phosphate and be dissolved in the deionized water, then in mixed solution, add 1.2mol resorcinol and 0.45mol polyethylene glycol (PEG-2000), mix.Measure formalin, the mol ratio that makes formaldehyde and resorcinol is to add in mentioned solution at 2: 1.And under magnetic stirring apparatus, constantly stir, 35 ℃ of constant temperature stirred 6 hours, and to regulate the pH value with ammoniacal liquor be about 8.9, formed colloidal sol after the ultrasonic dispersion;
2) with behind the 160 ℃ of dry 5h of colloidal sol that make, solvent evaporated obtains xerogel;
3) ball milling 6h on planetary ball mill then, rotating speed is 600 rev/mins.Fully grind afterwards pre-burning 8h under 380 ℃ of temperature.The lower 700 ℃ of calcination 10h of nitrogen and hydrogen (5%-10%) atmosphere, gas flow is 0.1～10L/min.Cooling down can obtain powder LiFePO to room temperature
4/ C composite material.
Composite material with embodiment 1 gained is made electrode by the following method, and carries out battery pack dress and charge-discharge test.
With positive electrode LiFePO
4: acetylene black: binding agent=mix at 80: 10: 10, ball milling is even.Then be mixed into slurry with nmp solvent, be put on the aluminium foil with scraper is deposited, paint electrode, 120 ℃ of vacuumize 24h after the compacting of taking-up electrode slice, obtain the serondary lithium battery positive plate.With above-mentioned LiFePO
4/ C is positive electrode, and the pure metal lithium sheet is negative pole, and Celgard2400 is barrier film, 1mol/LLiPF
6EC/DMC solution be electrolyte.In being full of the glove box of argon gas, this electrode slice and metal lithium sheet are assembled into button 2032 type batteries, then do the constant current charge-discharge loop test at (the new Weir in Shenzhen Electronics Co., Ltd.) high accuracy battery test macro, can see on the discharge curve of voltage range 2.5～4.2V that battery has stably discharge voltage plateau at 3.4V.
Embodiment 2
1) takes by weighing 0.75mol lithium chloride, 0.95mol ferrous oxalate, 0.80mol lithium phosphate, be dissolved in the deionized water, then in mixed solution, add 1.56mol resorcinol and 0.65mol polyethylene glycol (PEG-2000), mix.Measure formalin, the mol ratio that makes formaldehyde and resorcinol is to add in mentioned solution at 2: 1.And under magnetic stirring apparatus, constantly stir, 55 ℃ of constant temperature stirred 5 hours, and were about 4.2 with the salt acid for adjusting pH value, formed colloidal sol after the ultrasonic dispersion;
2) with behind the 120 ℃ of dry 9h of colloidal sol that make, solvent evaporated obtains xerogel;
3) ball milling 10h on planetary ball mill then, rotating speed is 500 rev/mins.Fully grind afterwards pre-burning 5h under 450 ℃ of temperature.The lower 900 ℃ of calcination 5h of nitrogen and carbon monoxide (5%～10%) atmosphere, gas flow is 0.1～10L/min.Cooling down can obtain powder LiFePO to room temperature
4/ C composite material.
Make electrode according to the method step among the embodiment 1, and carry out battery pack dress and charge-discharge test.
Embodiment 3
1) takes by weighing 1.06mol lithium acetate, 1.36mol ironic citrate, 1.47mol ammonium phosphate and be dissolved in the deionized water, then in mixed solution, add 2.52mol resorcinol and 0.95mol polyethylene glycol (PEG-2000), mix.Measure formalin, the mol ratio that makes formaldehyde and resorcinol is to add in mentioned solution at 2: 1.And under magnetic stirring apparatus, constantly stir, 80 ℃ of constant temperature stirred 2 hours, and were about 6.9 with the different proportion adjusting pH value of ammoniacal liquor and hydrochloric acid, formed colloidal sol after the ultrasonic dispersion;
2) with behind the 90 ℃ of dry 20h of colloidal sol that make, solvent evaporated obtains xerogel;
3) ball milling 3h on planetary ball mill then, rotating speed is 600 rev/mins.Fully grind afterwards pre-burning 10h under 300 ℃ of temperature.The lower 650 ℃ of calcination 10h of nitrogen and hydrogen (5%～10%) protective atmosphere, gas flow is 0.1～10L/min.Cooling down can obtain powder LiFePO to room temperature
4/ C composite material.
Make electrode according to the method step among the embodiment 1, and carry out battery pack dress and charge-discharge test.
Claims (1)
1. lithium ion battery composite cathode material LiFePO
4The preparation method of/C, take lithium salts, molysite and phosphate as raw material, comprise mixing, reaction, drying, ball milling, calcining and cooling, it is characterized in that: with lithium salts, molysite, phosphate, resorcinol and PEG in molar ratio 0.85～1.45: 0.95～1.60: 0.8～1.50: 1.5～2.8: 0.75～1.65 mix soluble in water, add at last formalin, the mol ratio of formaldehyde and resorcinol 2: 1, lower stir and transfer pH 3.5～10.5 in 30～80 ℃, react under the ultrasonic dispersion condition simultaneously and made colloidal sol in 2～6 hours; In 300～450 ℃ of lower pre-burnings 5～10 hours, under reducing atmosphere, made LiFePO in 4～16 hours in 600～900 ℃ of calcinings at last behind drying sol, the ball milling
4/ C positive electrode; Described lithium salts is selected from lithium hydroxide, lithium chloride or lithium acetate; Described molysite is selected from frerrous chloride, ferrous oxalate or ironic citrate; Described phosphate is selected from lithium phosphate, ammonium phosphate or diammonium hydrogen phosphate; Described reducing atmosphere is the gaseous mixture of hydrogen or carbon monoxide and argon gas or nitrogen; Described pH value 3.5～10.5th is transferred pH3.5～6.4 or is transferred pH7.5～10.5 or transfer pH6.5～7.4 with hydrochloric acid, ammoniacal liquor with ammoniacal liquor with hydrochloric acid.
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| CN102110811B (en) * | 2011-01-14 | 2012-11-14 | 浙江大学 | Method for preparing nanoscale lithium ion battery LiFePo4/C anodal material |
| CN102437314B (en) * | 2011-12-07 | 2013-10-09 | 哈尔滨工业大学 | Foam metal/lithium iron phosphate integral electrode with three-dimensional structure, preparation method thereof and lithium ion battery using integral electrode as positive pole piece |
| CN102655233B (en) * | 2011-12-14 | 2014-05-07 | 中聚电池研究院有限公司 | Preparation method of LiFePO4/C anode material of lithium ion battery |
| CN102916169B (en) * | 2012-10-26 | 2015-05-13 | 中国科学院宁波材料技术与工程研究所 | Lithium-rich manganese-based anode material and method for manufacturing same |
| CN104319400A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of nano spinel-type lithium manganate |
| CN104319399A (en) * | 2014-10-11 | 2015-01-28 | 柳州豪祥特科技有限公司 | Preparation method of modified nickel-doped lithium manganate |
| CN106207173B (en) * | 2016-08-31 | 2018-07-10 | 山东精工电子科技有限公司 | A kind of method that lithium iron phosphate positive material is prepared based on colloid skeleton |
| CN106654264A (en) * | 2017-01-12 | 2017-05-10 | 吉林大学 | Solvothermal assisted preparation method of LiFePO4/C multistage composite microspheres |
| CN106887586B (en) * | 2017-03-17 | 2018-11-20 | 江苏贝肯新材料有限公司 | A kind of the iron manganese phosphate electrode material of lithium battery and preparation method of carbon aerogels network |
| CN115050582A (en) * | 2022-06-20 | 2022-09-13 | 天津科技大学 | Porous carbon support composite lithium extraction electrode and preparation method thereof |
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