CN102263236B - Preparation method of meso-porous spherical lithium iron phosphate/carbon in-situ composite material - Google Patents

Preparation method of meso-porous spherical lithium iron phosphate/carbon in-situ composite material Download PDF

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CN102263236B
CN102263236B CN2011101645611A CN201110164561A CN102263236B CN 102263236 B CN102263236 B CN 102263236B CN 2011101645611 A CN2011101645611 A CN 2011101645611A CN 201110164561 A CN201110164561 A CN 201110164561A CN 102263236 B CN102263236 B CN 102263236B
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CN102263236A (en
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张旭东
何文
张学广
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Shandong Institute of Light Industry
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Abstract

The invention relates to a preparation method of a meso-porous spherical lithium iron phosphate/carbon in-situ composite material of a positive electrode material of a lithium ion battery, which comprises the following steps of: preparing a microorganism solution by using low-cost yeast, adding a phosphorus source, then adding an iron source, a reducing agent and a lithium source, water-bathing and aging to obtain gel; after drying, obtaining a lithium iron phosphate precursor; carrying out heating treatment on the lithium iron phosphate precursor to obtain meso-porous spherical lithium iron phosphate/carbon in-situ composite material powder. The meso-porous spherical lithium iron phosphate/carbon in-situ composite material can increase the electrochemistry performance of the positive electrode material of a lithium iron phosphate/carbon campsite lithium ion battery and can be used for preparing portable power lithium ion batteries.

Description

The preparation method of a kind of mesoporous sphere LiFePO4/carbon in-situ composite
(1) technical field
The present invention relates to a kind of lithium ion battery anode material lithium iron phosphate/carbon in-situ composite (LiFePO with mesoporous sphere structure and superperformance 4/ C) preparation method belongs to technical field of function materials.
(2) background technology
LiFePO4 (LiFePO 4) as the lithium ion battery novel anode material, although difficulty, electric conductivity and conductibility are poor in preparation, its fail safe and Heat stability is good, low price, non-environmental-pollution, and efficiency for charge-discharge height.Therefore, LiFePO 4Caused that domestic and international people pay close attention to greatly, be considered to have the lithium ion battery material of application potential, in particular as the positive electrode of power lithium-ion battery.
At present, prior art for preparing LiFePO 4Several different methods is arranged, and Goodenough etc. adopt the synthetic LiFePO of high temperature solid-state method 4Referring to: Padhi A K, Nanjundaswamy K S, Goodenough J B.Phospho-olivines as positive-electrode materials for rechargeable lithium batteries[J] Journal of the Electrochemical Society, 1997,144 (4): 1188-1194..This method is simple and convenient, operation easily, but have long, the shortcomings such as product batch quality stability is poor, cost height of synthesis cycle.Prosini etc. adopt the synthetic LiFePO of coprecipitation 4Referring to: Prosini P P, Carewska M, Scaccia S, et al.A new synthetic route for preparing LiFePO4 with enhanced electrochemical performance[J] .Journal of the Electrochemical Society, 2002,149 (7): this method component of 886-890. is even, synthesis temperature is low, particle is thin, but tap density is little, seriously polluted; Croce etc. adopt the synthetic LiFePO of sol-gel process 4Referring to: Croce F, Epifanio A D, Hassoun J, et al.A novel concept for the synthesis of an improved LiFePO4lithium battery cathode[J] Electrochemical and Solid-State Letters, 2002,5 (3): this method chemical uniformity of 47-50. is good, heat treatment temperature is low, particle diameter is little and narrowly distributing, be easy to control, but dry shrink big, suitability for industrialized production is difficult, synthesis cycle is long; Kaoru D etc. adopt the synthetic LiFePO of hydro thermal method 4Referring to: Kaoru D, Shohei K, Keisuke S, et al.Electrochemical properties of LiFePO4 prepared via hydrothermal route[J] Journal of Power Sources, 2007,165 (2): this method of 656-659. has thing phase homogeneous, little, the simple advantage of building-up process of diameter of particle, but be only limited to a small amount of powder preparing, need high-temperature high-pressure apparatus, the cost height.Zhang Bao etc. adopt the synthetic LiFePO of carbothermic method 4Referring to: open precious, Li Xinhai, ZhuBing Quan etc. precipitation-carbon thermal reduction combination method prepares olivine LiFePO4 [J]. China YouSe Acta Metallurgica Sinica, 2006,16 (8): 1445-1449, this method has overcome the high shortcoming of solid phase method cost, can improve material conductivity, but the reaction time is long, the product lack of homogeneity, particle is thicker.
In addition, relevant at present synthetic LiFePO 4Material also has some patent documents open, for example, CN101339995A discloses " preparation method of lithium iron phosphate positive electrode material for lithium ion power cell ", this method passes through to add micro-nano-metal-oxide or slaine, and adopts water system wet-mixed, spray drying, the synthetic LiFePO of roll extrusion granulating technique 4CN1635648A discloses " preparation method of high-density spherical ferric lithium phosphate as anode material of lithium-ion battery ", this method is at first by wet-chemical reaction synthesizing spherical or class ball shape ferric phosphate precursor, evenly mix with lithium source, carbon source, doping metals compound then, reducing atmosphere heat treatment obtains spherical LiFePO 4.More than research and patent document mainly concentrate on the improvement and the LiFePO of existing synthetic method 4The modification aspect, do not make LiFePO 4The synthetic technology of material, aspect of performance produce substantial variation, therefore, and synthetic LiFePO 4The needs that are difficult to satisfy electrokinetic cell because of combination property is undesirable.At present, according to the market demand of lithium ion battery, be badly in need of on synthetic technology, having new breakthrough both at home and abroad, in the hope of further improving LiFePO 4Combination properties such as conductivity, conductivity, reduce synthetic cost, thereby satisfy the needs of new energy field anode material for lithium-ion batteries.
(3) summary of the invention
In order to solve lithium ion battery anode material lithium iron phosphate conductivity and the low problem of conductivity that prior art exists, the invention provides a kind of mesoporous sphere structure lithium iron phosphate/carbon (LiFePO with good combination property 4/ C) the synthetic method of in-situ composite.
The present invention combines biotechnology to realize the object of the invention with chemical synthesis process.
Technical scheme of the present invention is as follows:
A kind of anode material for lithium-ion batteries mesoporous sphere LiFePO4/carbon (LiFePO 4/ C) the preparation method of in-situ composite, step is as follows:
(1) microbe is dissolved in the deionized water, under 42 ℃ of conditions, cultivated 20～30 minutes, solution is filtered purifying, make that microbial cell concentration is 4 * 10 in the solution 7Individual/ml～5 * 10 7Individual/ml, be designated as A solution;
(2) in A solution, add phosphorus source (PO 4 3+) and to make its concentration in A solution be 0.5mol/L, stirs 1h, is designated as B solution; Under stirring condition, press LiFePO 4Stoichiometric proportion is respectively that the ferric salt solution of 0.5～1.0mol/L and reductant solution that concentration is 1.0～2.0mol/L join in the B solution with concentration, and fully stirs 0.5～1h under 50～70 ℃, is designated as C solution.
(3) press LiFePO 4Stoichiometric proportion adds lithium ion (Li in C solution +) concentration is the lithium source (Li of 0.8mol/L +), regulating its pH with concentration for 10mol/L ammoniacal liquor is 6, fully stirs 1～3h.Ageing 16～24h under 60～90 ℃ of water bath condition gets gel.
(4) gel that step (3) is obtained gets ferric lithium phosphate precursor in 70～150 ℃ of down dry 10～24h.
(5),, obtain mesoporous sphere LiFePO4/carbon (LiFePO behind 280～300 ℃ of heat treatment 3～3.5h, being warming up to 500～900 ℃ of heat treatment 2～5h under the nitrogen atmosphere condition again with above-mentioned ferric lithium phosphate precursor 4/ C) composite material powder.
According to the present invention, preferred, the microbe in the step (1) is Saccharomyces cerevisiae or brewer's yeast.
According to the present invention, preferred, solution is that Saccharomyces cerevisiae or brewer's yeast are dissolved in the deionized water in the step (1), cultivates 25 minutes under 42 ℃ of conditions, and barm cell concentration is 4.5x10 in the solution 7Individual/ml.
According to the present invention, preferred, the described PO in the step (2) 4 3+The source is ammonium dihydrogen phosphate, diammonium hydrogen phosphate or phosphoric acid; Special preferably phosphoric acid ammonium dihydrogen.
According to the present invention, preferred, trivalent iron salt is a ferric nitrate described in the step (2), and described reducing agent is citric acid or oxalic acid.
According to the present invention, preferred, the mol ratio of trivalent iron salt and reducing agent is 1: 2 in the step (2).
According to the present invention, preferred, Li described in the step (3) +The source is lithium nitrate, lithium carbonate, lithium acetate, lithium formate or lithium hydroxide; Preferred especially lithium nitrate.
According to the present invention, preferred, ferric lithium phosphate precursor obtains mesoporous sphere LiFePO4/carbon (LiFePO be warming up to 750 ℃ of insulation 3h under the nitrogen atmosphere condition again behind 300 ℃ of heat treatment 3h in the step (5) 4/ C) composite material powder.
The present invention with the technical scheme of embodiment 1 as scheme most preferably.
Adopt the inventive method, key technology is that microbial technique is combined with sol-gel technique, source of iron, phosphorus source, lithium source are mixed with yeast microorganism solution, make ionic adsorption to the Saccharomyces globosus cell, form stable granule, thereby realize that LiFePO4 synthesizes the bionical of microbe with coating layer.Yeast has not only played the effect of formation mesoporous sphere stay in place form in bionical building-up process, and for preparation LiFePO4/carbon in-situ composite provides carbon source, thereby improved the chemical property of lithium iron phosphate.
Mesoporous sphere LiFePO4/carbon (LiFePO that the inventive method is prepared 4/ C) the composite granule particle is spherical in shape, and particle diameter is 6～12 microns; Have meso-hole structure, mesoporous aperture is about 2～20nm, and porosity is about 10～15%, shown in Fig. 2-4; Chemical property is good, and conductance is 1.8～2.5 * 10 -3S/cm, specific discharge capacity can reach 148～165mAh/g, and the first discharge specific capacity conservation rate is 82～95%.
Compared with the prior art, advantage of the present invention is that utilizing cheap microbe is mesoporous template and carbon source, adopt simple microbe-collosol and gel synthesis technique, bionically synthesized well behaved LiFePO4/carbon original position anode material for compound lithium ion battery with mesoporous sphere structure.LiFePO4/carbon original position composite granule with the present invention's preparation can be used for preparing portable and power lithium-ion battery as positive electrode.
(4) description of drawings
Fig. 1 is the XRD analysis of embodiment 1 synthetic powder;
Fig. 2 is the ESEM picture (a-c) of embodiment 1 synthetic powder different amplification;
Fig. 3 is the nitrogen adsorption desorption isothermal curve (a) of embodiment 1 synthetic powder;
Fig. 4 is the pore size distribution curve (b) of embodiment 1 synthetic powder.
(5) embodiment
The present invention will be further described below in conjunction with embodiment, but be not limited thereto.Used Saccharomyces cerevisiae numbering 80000109 among the embodiment, Angel Yeast Co.,Ltd's product; Brewer's yeast numbering FFX-0009, Dongguan Lv Yuan fruit and vegetable product Co., Ltd product.
Embodiment 1
Saccharomyces cerevisiae is dissolved in the deionized water, cultivated 25 minutes down in 42 ℃, filter purifying and microbial solution, barm cell concentration is 4.5x10 in the control solution 7Individual/ml, be designated as A solution.Adding ammonium dihydrogen phosphate and make its concentration in A solution in A solution is 0.5mol/L, stirs 1h, is designated as B solution.Under stirring condition, press LiFePO 4Stoichiometric proportion is that the iron nitrate solution of 0.8mol/L joins in the B solution with concentration, presses 1: 2 mol ratio of ferric nitrate and citric acid, is that the citric acid solution of 1.6mol/L joins in the B solution with concentration, and fully stirs 0.5h under 70 ℃, is designated as C solution.Press LiFePO 4Stoichiometric proportion adds the 0.8mol/L lithium nitrate solution in C solution, regulating mixed solution pH with 10mol/L ammoniacal liquor is 6, fully stirs 2h, and ageing 20h under 80 ℃ of water bath condition forms gel.With gel dry 16h under 100 ℃, obtain ferric lithium phosphate precursor.With ferric lithium phosphate precursor grind the back under the nitrogen atmosphere protection in 300 ℃ of heat treatment 3h, be warmed up to 750 ℃ of insulation 3h again, obtain black powder.Through X-ray diffraction analysis is olivine-type LiFePO 4The complex of/C, as shown in Figure 1.By SEM and adsorption-desorption isothermal curve and pore size distribution curve analysis as can be known, LiFePO4/carbon composite powder particle is spherical in shape, and particle diameter is 6～12 microns; Have meso-hole structure, mesoporous aperture is about 2～20nm, and porosity 12% is as Fig. 2, Fig. 3, shown in Figure 4; Gained LiFePO4/carbon composite powder is made positive pole and is assembled into battery, and after measured, its conductance is 2.5 * 10 -3S/cm, specific discharge capacity can reach 165mAh/g, and the first discharge specific capacity conservation rate is 95%.
Embodiment 2
Saccharomyces cerevisiae is dissolved in the deionized water, cultivated 30 minutes down in 42 ℃, after filtration purifying and microbial solution, barm cell concentration is 5x10 in the control solution 7Individual/ml, be designated as A solution.Adding ammonium dihydrogen phosphate and make its concentration in A solution in A solution is 0.5mol/L, stirs 1h, is designated as B solution.Under stirring condition, press LiFePO 41: 2 mol ratio of stoichiometric proportion and ferric nitrate and citric acid is respectively that the iron nitrate solution of 1.0mol/L and citric acid solution that concentration is 2.0mol/L join in the B solution with concentration, and fully stirs 0.7h under 60 ℃, is designated as C solution.Press LiFePO 4Stoichiometric proportion adds 0.8mol/L lithium acetate solution in C solution, regulating mixed solution pH with 10mol/L ammoniacal liquor is 6, fully stirs 3h, and ageing 24h under 60 ℃ of water bath condition forms gel.With gel dry 24h under 70 ℃, obtain ferric lithium phosphate precursor.With ferric lithium phosphate precursor grind the back under the nitrogen atmosphere protection in 280 ℃ of heat treatment 3.5h, be warmed up to 500 ℃ of insulation 5h again, obtain black powder LiFePO4/carbon composite powder.
Embodiment 3
Brewer's yeast is dissolved in the deionized water, cultivated 20 minutes down in 42 ℃, filter behind the purifying and microbial solution, barm cell concentration is 4x10 in the control solution 7Individual/ml, be designated as A solution.Adding ammonium dihydrogen phosphate and make its concentration in A solution in A solution is 0.5mol/L, stirs 1h, is designated as B solution.Under stirring condition, press LiFePO 41: 2 mol ratio of stoichiometric proportion and ferric nitrate and citric acid is respectively that the iron nitrate solution of 0.5mol/L and citric acid solution that concentration is 1.0mol/L join in the B solution with concentration, and fully stirs 1h under 50 ℃, is designated as C solution.Press LiFePO 4Stoichiometric proportion adds the 0.8mol/L lithium hydroxide solution in C solution, regulating mixed solution pH with 10mol/L ammoniacal liquor is 6, fully stirs 1h, and ageing 16h under 90 ℃ of water bath condition forms gel.With gel dry 10h under 150 ℃, obtain ferric lithium phosphate precursor.With ferric lithium phosphate precursor grind the back under the nitrogen atmosphere protection in 300 ℃ of heat treatment 3h, be warmed up to 900 ℃ of insulation 2h again, obtain black powder LiFePO4/carbon composite powder.

Claims (1)

1. the preparation method of anode material for lithium-ion batteries mesoporous sphere LiFePO4/carbon in-situ composite, step is as follows:
(1) Saccharomyces cerevisiae is dissolved in the deionized water, under 42 ℃ of conditions, cultivated 25 minutes, solution is filtered purifying, make that microbial cell concentration is 4.5x10 in the solution 7Individual/ml, be designated as A solution;
(2) in A solution, add ammonium dihydrogen phosphate and to make its concentration in A solution be 0.5mol/L, stir 1h, be designated as B solution; Under stirring condition, press LiFePO 4Stoichiometric proportion is respectively that the ferric nitrate salting liquid of 0.8mol/L and citric acid solution that concentration is 1.6mol/L join in the B solution with concentration, and fully stirs 0.5h under 70 ℃, is designated as C solution;
(3) press LiFePO 4Stoichiometric proportion, adding lithium concentration in C solution is the lithium nitrate solution of 0.8mol/L, regulating its pH with concentration for 10mol/L ammoniacal liquor is 6, fully stirs 3h; Ageing 20h under 80 ℃ of water bath condition gets gel;
(4) gel that step (3) is obtained dry 16h under 100 ℃ gets ferric lithium phosphate precursor;
(5),, obtain mesoporous sphere lithium iron phosphate powder behind 300 ℃ of heat treatment 3h, being warming up to 750 ℃ of heat treatment 3h under the nitrogen atmosphere condition again with above-mentioned ferric lithium phosphate precursor.
CN2011101645611A 2011-06-17 2011-06-17 Preparation method of meso-porous spherical lithium iron phosphate/carbon in-situ composite material Expired - Fee Related CN102263236B (en)

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CN105375031A (en) * 2013-08-30 2016-03-02 苏州宝时得电动工具有限公司 Lithium-ion battery positive electrode material preparation method
CN103840138B (en) * 2014-01-26 2016-03-02 浙江工业大学 A kind of utilize algae obtained Sn/C composite material and application
CN104201351B (en) * 2014-08-22 2017-01-11 武汉理工大学 Li2FeSiO4/C composite anode material with mesoporous microsphere structure and preparation method
CN109768256A (en) * 2019-01-18 2019-05-17 兰州理工大学 It is a kind of to prepare uniformly carbon-coated LiFePO with saccharomycete4The method of nanocomposite
CN113363463B (en) * 2021-06-02 2022-06-14 湖北亿纬动力有限公司 Sludge/biomass co-pyrolysis coke-coated lithium iron phosphate cathode material and preparation method and application thereof

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