CN101789504A - Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material - Google Patents

Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material Download PDF

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CN101789504A
CN101789504A CN201010126409A CN201010126409A CN101789504A CN 101789504 A CN101789504 A CN 101789504A CN 201010126409 A CN201010126409 A CN 201010126409A CN 201010126409 A CN201010126409 A CN 201010126409A CN 101789504 A CN101789504 A CN 101789504A
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positive pole
composite positive
lithium
iron powder
preparation
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CN101789504B (en
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胡国荣
曹雁冰
彭忠东
杜柯
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SICHUAN HOPEREADY NEW ENERGY MATERIAL CO., LTD.
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Central South University
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Abstract

The invention relates to a preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material. Lithium dihydrogen phosphate, iron powder, an M element source and an organic carbon source are uniformly mixed in a solvent medium, are treated for 2 to 7h through a high-energy ball mill, have chemical reaction under mechanical activation, and a uniformly dispersed precursor is prepared. The precursor is thermally treated for 2 to 10h at 600 to 800 DEG C under atmosphere protection and cooled to be room temperature, and the nano LiFel-xMxPO4/C lithium phosphate composite positive pole material is prepared. The preparation method has simple and high-efficiency process and the whole process does not produce ammonia, wastewater and other polluting substances, and is applicable to industrial production. The primary particles of the prepared material are nano particles which are uniformly distributed, and the material is characterized by high specific capacity and good rate cycle performance.

Description

A kind of nanoscale LiFe 1-xM xPO 4The preparation method of the phosphate-based composite positive pole of/C lithium
Technical field
The invention belongs to the anode material for lithium-ion batteries preparing technical field, related to the phosphate-based LiFe of a kind of nanoscale lithium 1-xM xPO 4The preparation method of/C composite positive pole.
Background technology
Pay close attention to along with global energy crisis and environmental issue more and more are subjected to common people, power-type lithium ion battery is more and more good by global battery industry and related industry.And positive electrode is the key component of power-type lithium ion battery, and the raising of its performance and the reduction of cost directly influence the whole power battery industry.Therefore it is most important to motive force of development battery industry to seek cheapness, stable performance, safety, eco-friendly cell positive material.The lithium phosphate material LiMePO of olivine structural 4(Me=Fe 2+, Co 2+, Ni 2+, Mn 2+) receive much concern because it has highly stable thermodynamic behaviour.Wherein, be representative with the LiFePO4, the raw material mineral resources is abundant, cheap, has the very high market competitiveness, has now become the most potential lithium-ion-power cell material.The main obstacle that the restriction phosphate material is used is that its electron conduction is poor, and the lithium ion diffusion coefficient is little, and it is bigger to make it when heavy-current discharge capacity attenuation.For addressing the above problem, improve lithium phosphate material performance at present and mainly pass through: carbon coats the preparation composite material; Or reduce the particle diameter of product by suitable preparation technology; Or, improve its chemical property to a certain extent by the synthetic defect semiconductor in metal ion replacement Li position or Fe position.
The high temperature solid-state method that generally adopts synthesizes phosphate material at present.Such as LiFePO 4Synthesizing of material; the organic molysite of divalence is mixed with ammonium hydrogen phosphate and lithium salts; under inert atmosphere protection, obtain product, can produce ammonia in this method sintering process and be unfavorable for environmental protection, and the organic molysite decomposition of divalence can produce the tap density that a large amount of gases reduce product through high-temperature calcination.People such as Zhang propose with LiH 2PO 4, FeC 2O 42H 2O and carbon dust are the synthetic LiFePO of raw material 4Material [S.S.Zhang, J.L.Allen, K.Xu, et al.Optimization of reactioncondition for solid-state synthesis of LiFePO4-C composite cathodes.Journal of Power Sources, 2005,147:234-240], the product crystal grain of high temperature solid-state method is bigger than normal, be difficult to control the uniformity of product component, discharge capacity is 127mAhg under the 0.1C multiplying power -1, be unfavorable for preparing the good material of multiplying power cycle performance.J.Barker etc. have proposed LiH 2PO 4, Fe 2O 3With carbon dust be the synthetic LiFePO of raw material 4Carbothermic method [Swoyer J L, Barker J, Saidi M Y.Lithium iron (II) phospho-olivines prepared by anovel carbothermal reduction method.Electrochemical and Solid-StateLetters, 2003,6 (3): A53～A55], in fact also be high temperature solid state reaction.In the carbothermic reduction reaction process, can produce a large amount of CO gases, also exist long or product granular size of reaction time to be difficult to shortcomings such as control.
Softening methods such as sol-gel process, hydro thermal method, liquid phase coprecipitation can prepare the less lithium phosphate material of particle diameter.Yet sol-gal process suitability for industrialized production difficulty is big, synthesis cycle is longer; Hydro thermal method is only limited to a spot of powder preparing, and large-scale high temperature high voltage resistant DESIGN OF REACTOR manufacture difficulty is big, and cost is also high; Liquid phase coprecipitation technology is complicated, and producing the waste water that generally contains foreign ion in the process needs to handle.
Patent CN200810207542.0 discloses a kind of carbon-coated LiFePO 4 for lithium ion batteries (LiFePO 4/ C) coprecipitation method, in reaction vessel, add a certain amount of deionized water, phosphoric acid, be heated to 70～90 ℃, add iron powder and carbon source, under agitation react 5h, slowly drip lithium hydroxide solution subsequently, reaction 4h, obtain presoma after adopting spray-dired method with the product drying then, whole process is finished under the condition of logical nitrogen.Presoma is transferred in the tube furnace handling 6～24h under 750 ℃ of temperature again after the preliminary treatment under 200 ℃ of temperature and is obtained described carbon-coated LiFePO 4 for lithium ion batteries, and specific discharge capacity is 136.8 under the 0.2C multiplying power, specific discharge capacity 128.1mAhg under the 1C multiplying power -1But this kind method is raw material with phosphoric acid, and the fluctuation of phosphorus component content is big, produces in the actual mechanical process production stay in grade to meet the LiFePO4 that precise chemical structure is measured, and needs adjust the precursor prescription at any time, is unfavorable for industrialized mass production; Related co-precipitation synthetic method, adopt the reaction of phosphoric acid and iron powder, the phosphate that generates indissoluble can form nucleus and grows up and cover reactant gradually at reaction-ure surface, stop reaction further to be carried out, need long-time reaction, temperature required height also needs follow-up interpolation lithium source, the processing step complexity.
Summary of the invention
Purpose of the present invention aims to provide the phosphate-based LiFe of a kind of nanoscale lithium 1-xM xPO 4The preparation method of/C composite positive pole, this method have lower synthetic cost, can improve the ion-electron conductivity that improves the lithium phosphate material, make it become high-energy-density, high-power anode material for lithium-ion batteries.
For achieving the above object, technical scheme of the present invention is the phosphate-based LiFe of nanoscale lithium of the present invention 1-xM xPO 4Preparation method's step of/C composite positive pole is as follows:
With LiH 2PO 4, iron powder, M element source and organic carbon source be blended in the ball-milling medium in proportion, mol ratio Li wherein: (Fe+M): P=1: 1: 1, organic carbon source according to target product carbon content 0.5～5wt% added.Behind mixture ball milling 2～7h, 70～120 ℃ of vacuumizes promptly get presoma.Presoma is heat-treated under inert gas shielding, and heat treatment temperature is 600～800 ℃, and the time is 2～10h, is cooled to room temperature and obtains nanoscale LiFe 1-xM xThe PO4/C composite positive pole.
Described LiFe 1-xM xPO 40≤x in the/C molecular formula≤0.5; Described M element is that Li, Mn, Ni, Co, Cu, Cr, V, Si, Nb are at least a.Described iron powder is at least a in reduced iron powder, the electrolytic iron powder, and below granularity 200 orders, purity is more than 98%.Described organic carbon source is at least a in glucose, sucrose, citric acid, starch, polyvinyl alcohol, polypropylene, the phenolic resin; Described ball-milling medium is deionized water or deionization water-ethanol blending agent; Described protective atmosphere is an argon gas, nitrogen, argon gas-hydrogen gas mixture, nitrogen-hydrogen gas mixture.
Positive electrode of the present invention becomes CR2025 type button cell to carry out the charge and discharge cycles test material.Adopt coating method to prepare electrode, with N-N-methyl-2-2-pyrrolidone N-(NMP) is solvent, respectively takes by weighing active material, acetylene black and PVDF at 8: 1: 1 by mass ratio, after mixing, be coated on the pretreated aluminium foil, put into vacuum drying chamber and obtain positive plate 120 ℃ of dryings.In being full of the glove box of argon gas, be negative pole with the metal lithium sheet, 1molL -1LiPF 6Being dissolved in ethylene carbonate (EC)+dimethyl carbonate (DMC)+ethyl-methyl carbonic ester (EMC) (volume ratio is 1: 1: 1) is electrolyte, the Celgard2400 porous polyethylene membrane is a barrier film, be assembled into button cell, on Land electrochemistry instrument, carry out electro-chemical test.
The present invention adopts simple process flow, with LiH 2PO 4As phosphorus source and lithium source, stable components helps the accurate control of precursor prescription, is beneficial to lithium, the formation of iron calcium phosphate precipitation; Adopt the mechanical activation technology to promote LiH 2PO 4React with metal dust, reaction raw materials is broken and the contact area of augmenting response, meanwhile the product cover layer of Xing Chenging is destroyed under the percussion and refinement forms more phosphate nucleus fully strong the grinding, reaction interface is brought in constant renewal in, improve the dynamic conditions of precipitation reaction fully, promoted successful reaction to carry out.The mechanical activation process also can make newly-generated presoma surface activity increase, and its particle of refinement promotes the carrying out of follow-up pyroreaction.
The present invention impels metal dust to remove to replace LiH by mechanical activation aids precipitation technology 2PO 4In hydrogen, generate Fe when iron powder dissolves gradually 3(PO 4) 2And Li 3PO 4Precipitation, M elemental substance then fellowship are reacted or are adsorbed on newborn sediment surface, obtain homodisperse presoma.The present invention can realize the mixing on molecular level of lithium, iron, phosphorus and doped chemical, obtained to have primary particle and be nanometer-size die, than the presoma of high reaction activity, help the diffusion of each component under the follow-up high temperature and the uniformity of control product component, shorten simultaneously crystallization time greatly, obtained the tiny product of particle size.Interpolation can be dispersed in the organic carbon source in the ball-milling medium in presoma is synthetic, can prevent the reunion of presoma.The carbon that organic carbon source decomposes in high-temperature process subsequently can be realized the original position of synthetic product is evenly coated, and effectively controls the grain growth of positive electrode, and forms the conductive carbon film that is interconnected between particle, prepares well behaved nanoscale LiFe 1-xM xPO 4/ C composite positive pole.
Compare with the material of patent CN200810207542.0 preparation in the background technology, the present invention adopts the positive electrode 0.2C～1C multiplying power discharging specific capacity of mechanical activation precipitation method preparation to be significantly improved, and the platform conservation rate is better, is 155mAhg as discharge capacity under the product 0.2C among the embodiment 1 -1, discharge capacity 140.5mAhg under the 1C -1
The present invention adopts the mechanical activation precipitation method to prepare the phosphate-based LiFe of nanoscale lithium 1-xM xPO 4/ C composite positive pole, it is as follows to have advantage:
(1) obtained the presoma that each component is evenly disperseed, particle is tiny, can prepare primary particle is the nanoscale positive electrode, shortens the diffusion length of Li ion, improves the lithium ion conductivity and the specific capacity of material.
(2) adopt metal ion to replace and carbon coating jointly modified technology, improve the conductivity of material and reduced electrode-electric and separated the liquid interface charge and shift resistance, improve the multiplying power cycle performance of material.
(3) technology is simple, and preparation process is efficient, clean environment firendly, and does not have pollutants such as ammonia, waste water to produce in the whole process, is beneficial to the realization industrialization.
Description of drawings
Fig. 1 is the x-ray diffraction pattern of sample.(a, embodiment 1 predecessor; B, embodiment 1 product; C embodiment 2 products; D, embodiment 4 products).
Fig. 2 is the phosphate-based LiFe of lithium 1-xM xPO 4/ C composite material Electronic Speculum figure.(a, the SEM figure of embodiment 2 products; B, the TEM of embodiment 3 products, c, regional enlarged drawing among the b figure).
Fig. 3 is that product is formed charging and discharging curve figure under the different multiplying of battery among the embodiment 1.
Fig. 4 charges and discharge curve chart for product among the embodiment 2 under the 3C multiplying power.
Fig. 5 charges and discharge curve chart for product among the embodiment 3 under the 2C multiplying power.
Fig. 6 is product cycle performance figure under 3C, 2C multiplying power respectively among embodiment 2, the embodiment 3.
Fig. 7 charges and discharge curve chart for product among the embodiment 4 under the 0.2C multiplying power.
Fig. 8 charges and discharge curve chart for product among the embodiment 5 under the 0.2C multiplying power.
Fig. 9 is product cycle performance figure under the 0.2C multiplying power among embodiment 4, the embodiment 5.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Lithium dihydrogen phosphate, iron powder, copper acetate are taken by weighing according to mol ratio at 1: 0.98: 0.02, and the glucose of adding mixed material 5wt%, being dispersed in deionized water through high-energy ball milling 4h, 70 ℃ of vacuumizes obtain presomas, Fig. 1 a does not find iron powder and LiH for its XRD figure spectrum 2PO 4Diffraction maximum, but the product Li after the complete reaction 3PO 4And Fe 3(PO4) 2Place atmosphere furnace, 600 ℃ of calcining 10h are cooled to room temperature and have obtained the nanoscale LiFePO that copper mixes under argon shield 4/ C composite positive pole.Detect carbon containing 0.89wt% in this composite positive pole, XRD detects this material and has single olivine structural, under the 0.2C first discharge capacity be 154mAhg -1, discharge capacity 140.5mAhg under the 1C -1
Embodiment 2
With lithium dihydrogen phosphate, iron powder, lithium carbonate, vanadic oxide according to mol ratio 1: 0.95: 0.02: 0.005 takes by weighing, and adds the sucrose of mixed material 6wt%, is dispersed in deionized water through high-energy ball milling 5h, and 90 ℃ of vacuumizes obtain presomas.Place atmosphere furnace, 650 ℃ of calcining 6h are cooled to room temperature and have obtained the nanoscale LiFePO that lithium-vanadium mixes under argon shield 4/ C composite positive pole.Detect carbon containing 1.5wt% in this composite positive pole, find out under the high power SEM about even particle size 100nm, discharge capacity 130.2mAhg under 3C -1, basic not decay after 70 times circulates.
Embodiment 3
With lithium dihydrogen phosphate, iron powder, monohydrate lithium hydroxide, nano silicon according to mol ratio 1: 0.96: 0.03: 0.01 takes by weighing, and the polyvinyl alcohol of adding mixed material 10wt%, be dispersed in deionization water-ethanol blending agent through high-energy ball milling 6h, 110 ℃ of vacuumizes obtain presoma.Place atmosphere furnace, 700 ℃ of calcining 6h are cooled to the nanoscale LiFePO that room temperature has obtained lithium-silicon doping under argon shield 4/ C composite positive pole.Detect carbon containing 2.1wt% in this composite positive pole, from TEM as can be seen granular size be 50-100nm, exist the favorable conductive carbon film to connect between particle, discharge capacity 141mAhg under 2C -1, basic not decay after 70 times circulates.
Embodiment 4
With lithium dihydrogen phosphate, iron powder, manganese powder, nickel acetate according to mol ratio 1: 0.5: 0.45: 0.05 takes by weighing, and adds the starch of mixed material 15wt%, is dispersed in deionization water-ethanol blending agent through high-energy ball milling 7h, and 100 ℃ of vacuumizes obtain presomas.Place atmosphere furnace, 750 ℃ of calcining 4h are cooled to nanoscale LiFe (Mn, Ni) PO that room temperature has obtained multicomponent mixture under argon shield 4/ C composite positive pole.Detect carbon containing 4.7wt% in this composite positive pole, XRD detects this material and has single olivine structural, and multicomponent mixture has formed good solid solution, the interval discharge capacity 156mAhg of 2.5-4.5V under 0.2C -1, basic not decay after 50 times circulates.
Embodiment 5
With lithium dihydrogen phosphate, iron powder, manganese powder, cobalt acetate according to mol ratio 1: 0.5: 0.45: 0.05 takes by weighing, and adds the citric acid of mixed material 20wt%, is dispersed in the deionized water medium through high-energy ball milling 7h, and 70 ℃ of vacuumizes obtain presomas.Place atmosphere furnace, 700 ℃ of calcining 6h are cooled to nanoscale LiFe (Mn, Co) PO that room temperature has obtained multicomponent mixture under argon shield 4/ C composite positive pole.Detect carbon containing 3.9wt% in this composite positive pole, the interval discharge capacity 162mAhg of 2.5-4.5V under 0.2C -1, basic not decay after 50 times circulates.

Claims (5)

1. phosphate-based LiFe of nanoscale lithium 1-xM xPO 4The preparation method of/C composite positive pole is characterized in that, may further comprise the steps:
(1) with LiH 2PO 4, iron powder, M element source and organic carbon source be blended in the ball-milling medium in proportion, mol ratio Li wherein: (Fe+M): P=1: 1: 1, the addition of organic carbon source according to target product carbon content 0.5～5wt% added; Behind mixture high-energy ball milling processing 2～7h, 70～120 ℃ of vacuumizes promptly get presoma;
(2) presoma is heat-treated under inert gas shielding, heat treatment temperature is 600～800 ℃, and the time is 2～10h, is cooled to room temperature and obtains nanoscale LiFe 1-xM xThe PO4/C composite positive pole, 0≤x≤0.5; Described M element is that Li, Mn, Ni, Co, Cu, Cr, V, Si, Nb are at least a.
2. method according to claim 1 is characterized in that: described iron powder is at least a in reduced iron powder, the electrolytic iron powder, and below granularity 200 orders, purity is more than 98%.
3. method according to claim 1 is characterized in that: described organic carbon source is at least a in glucose, sucrose, citric acid, starch, polyvinyl alcohol, polypropylene, the phenolic resin.
4. method according to claim 1 is characterized in that: described ball-milling medium is deionized water or deionization water-ethanol blending agent.
5. method according to claim 1 is characterized in that: described protective atmosphere is an argon gas, nitrogen, argon gas-hydrogen gas mixture, nitrogen-hydrogen gas mixture.
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Cited By (14)

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CN102779979A (en) * 2011-05-13 2012-11-14 上海空间电源研究所 Method for preparing phosphoric acid cathode material of lithium battery
CN102810670A (en) * 2012-08-01 2012-12-05 因迪能源（苏州）有限公司 Composite anode material of lithium ion battery and preparation method
CN102983328A (en) * 2012-11-23 2013-03-20 清华大学 Method for preparing nanocrystalline lithium iron phosphate anode material from ferrous powder
CN103985868A (en) * 2014-05-28 2014-08-13 天津大学 Iron lithium manganese phosphate-carbon composite anode material for lithium ion battery and synthetic method of anode material
CN105355885A (en) * 2015-11-26 2016-02-24 中南大学 Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C
CN105514429A (en) * 2015-12-23 2016-04-20 邬石根 Technology for preparing composite electrode material with ball milling-high temperature calcination method
CN106356566A (en) * 2016-10-26 2017-01-25 新沂市中诺新材料科技有限公司 Lithium battery and preparation method thereof
CN107146877A (en) * 2017-05-03 2017-09-08 武汉理工大学 The preparation method and positive plate and lithium ion battery of a kind of fluorine oxygen phosphate lithium ion battery material
CN108455550A (en) * 2018-01-31 2018-08-28 贵州仁聚业科技股份有限公司 A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode
CN109742477A (en) * 2019-01-09 2019-05-10 东北师范大学 A kind of recovery method of waste and old ternary oxide anode
CN110828822A (en) * 2014-05-20 2020-02-21 美国政府(由美国陆军部长代表) High voltage lithium ion positive electrode material
CN112563469A (en) * 2020-12-09 2021-03-26 中南大学 Novel three-phase composite positive electrode material and preparation method thereof
CN113651303A (en) * 2021-08-13 2021-11-16 中南大学 Preparation method of nano flaky iron phosphate and LiFePO prepared by using same4Positive electrode active material/C
CN114566646A (en) * 2022-01-28 2022-05-31 上海兰钧新能源科技有限公司 Nickel-doped lithium manganese iron phosphate positive electrode material and preparation method and application thereof

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JP2007103298A (en) * 2005-10-07 2007-04-19 Toyota Central Res & Dev Lab Inc Positive electrode active material, its manufacturing method, and aqueous lithium secondary battery
CN1964105A (en) * 2006-11-27 2007-05-16 华南理工大学 Composite doping modification lithium-ion battery anode material and its manufacture method
CN101404328A (en) * 2008-10-30 2009-04-08 昆明理工大学 Preparation method of positive electrode material of lithium ion cell

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JP2007103298A (en) * 2005-10-07 2007-04-19 Toyota Central Res & Dev Lab Inc Positive electrode active material, its manufacturing method, and aqueous lithium secondary battery
CN1964105A (en) * 2006-11-27 2007-05-16 华南理工大学 Composite doping modification lithium-ion battery anode material and its manufacture method
CN101404328A (en) * 2008-10-30 2009-04-08 昆明理工大学 Preparation method of positive electrode material of lithium ion cell

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CN102779979A (en) * 2011-05-13 2012-11-14 上海空间电源研究所 Method for preparing phosphoric acid cathode material of lithium battery
CN102810670A (en) * 2012-08-01 2012-12-05 因迪能源（苏州）有限公司 Composite anode material of lithium ion battery and preparation method
CN102810670B (en) * 2012-08-01 2015-03-04 因迪能源（苏州）有限公司 Composite anode material of lithium ion battery and preparation method
CN102983328A (en) * 2012-11-23 2013-03-20 清华大学 Method for preparing nanocrystalline lithium iron phosphate anode material from ferrous powder
CN110828822B (en) * 2014-05-20 2023-08-18 美国政府(由美国陆军部长代表) High voltage lithium ion positive electrode material
CN110828822A (en) * 2014-05-20 2020-02-21 美国政府(由美国陆军部长代表) High voltage lithium ion positive electrode material
CN103985868A (en) * 2014-05-28 2014-08-13 天津大学 Iron lithium manganese phosphate-carbon composite anode material for lithium ion battery and synthetic method of anode material
CN105355885A (en) * 2015-11-26 2016-02-24 中南大学 Synthesis method of lithium ion battery composite cathode material LiMn1-xFexPO4/C
CN105514429A (en) * 2015-12-23 2016-04-20 邬石根 Technology for preparing composite electrode material with ball milling-high temperature calcination method
CN106356566B (en) * 2016-10-26 2018-10-09 河源市东聚能源科技有限公司 A kind of lithium battery and preparation method thereof
CN106356566A (en) * 2016-10-26 2017-01-25 新沂市中诺新材料科技有限公司 Lithium battery and preparation method thereof
CN107146877A (en) * 2017-05-03 2017-09-08 武汉理工大学 The preparation method and positive plate and lithium ion battery of a kind of fluorine oxygen phosphate lithium ion battery material
CN108455550A (en) * 2018-01-31 2018-08-28 贵州仁聚业科技股份有限公司 A kind of method that vacuum prepares lithium-ion battery lithium iron phosphate positive electrode
CN109742477A (en) * 2019-01-09 2019-05-10 东北师范大学 A kind of recovery method of waste and old ternary oxide anode
CN109742477B (en) * 2019-01-09 2020-10-13 东北师范大学 Method for recovering waste ternary oxide positive electrode
CN112563469A (en) * 2020-12-09 2021-03-26 中南大学 Novel three-phase composite positive electrode material and preparation method thereof
CN113651303A (en) * 2021-08-13 2021-11-16 中南大学 Preparation method of nano flaky iron phosphate and LiFePO prepared by using same4Positive electrode active material/C
CN113651303B (en) * 2021-08-13 2023-10-20 中南大学 Preparation method of nano flaky ferric phosphate and LiFePO prepared by using same 4 C positive electrode active material
CN114566646A (en) * 2022-01-28 2022-05-31 上海兰钧新能源科技有限公司 Nickel-doped lithium manganese iron phosphate positive electrode material and preparation method and application thereof
CN114566646B (en) * 2022-01-28 2024-01-16 上海兰钧新能源科技有限公司 Nickel-doped lithium iron manganese phosphate positive electrode material and preparation method and application thereof

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