CN103996823B - A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode - Google Patents

A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode Download PDF

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CN103996823B
CN103996823B CN201410192405.XA CN201410192405A CN103996823B CN 103996823 B CN103996823 B CN 103996823B CN 201410192405 A CN201410192405 A CN 201410192405A CN 103996823 B CN103996823 B CN 103996823B
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phosphate
carbon
lithium
salt
cobalt
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CN103996823A (en
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栗欢欢
王亚平
陈龙
江浩斌
李云星
陈依
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Jiangsu University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/5825Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/362Composites
    • H01M4/364Composites as mixtures
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection 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
    • H01M4/583Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00Batteries for particular applications
    • H01M2220/20Batteries in motive systems, e.g. vehicle, ship, plane
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides the rapid microwave reaction method for preparing of a kind of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode, 1~1.1:1/3:1/3:1/3:1 weigh lithium salts in molar ratio, iron salt, manganese salt, cobalt salt, phosphate are put into ball grinder and add people 7~10wt% carbon source, ball milling 5~10h, after drying, tabletting, inert atmosphere stove decomposes at 350 DEG C 1~5h;Grind again, tabletting, in microwave reactor, microwave 7~15min, obtain LiCo1/3Mn1/ 3Fe1/3PO4/C.The inventive method is simple, easily controllable, the response time is short, low cost.The LiCo of preparation1/3Mn1/3Fe1/3PO4Particle diameter is little, be evenly distributed, and electrical conductivity is high, has high specific capacity, good cycling stability, big multiplying power discharging property is excellent, energy density is high.

Description

A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode
Technical field
The present invention relates to the preparation of power lithium-ion battery positive electrode, be specifically related to the rapid microwave reaction method for preparing of a kind of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode.
Background technology
In recent years, along with the commercialized development of electric automobile, hybrid vehicle, a new generation's electric bicycle etc., lithium ion battery is faced with increasing challenge.Exploitation height ratio capacity, high power, long circulation life and low cost lithium ion battery become the Main way of its development.LiFePO4 (LiFePO4) positive electrode has that theoretical capacity height, low cost, safety be good, environmental friendliness and the feature such as multiplying power property is good, is one of the main selection of lithium-ion-power cell.But, it runs into some problems in actual applications, such as relatively low plateau potential (3.4V) and little tap density (owing to being coated with substantial amounts of carbon), therefore its specific energy density relatively low (about 580Wh/kg).Lithium manganese phosphate (LiMnPO4) and cobalt phosphate lithium (LiCoPO4) have and LiFePO4Similar olivine-type structure, but it has higher plateau potential (respectively 4.1V and 4.8V), and and LiFePO4The most suitable theoretical specific capacity (170mAh/g), therefore they compare LiFePO4There is the highest specific energy density (being about 684Wh/kg and 800Wh/kg respectively).But, due to LiMnPO4Electronic conductivity and ionic conductivity relatively low, therefore its electro-chemical activity is poor.And LiCoPO4Higher plateau potential so that conventional organic electrolyte decomposes, and therefore cycle performance is poor.
Three metal phosphate solid solution LiCo1/3Mn1/3Fe1/3PO4There are three charge and discharge radio station platforms, respectively 3.6V, 4.1V, 4.7V correspondences Fe2+/Fe3+、Mn2+/Mn3+And Co2+/Co3+Electrode potential, researcher find, the platform of Fe rises about 0.2V, and the platform of cobalt have dropped about about 0.2V, and the platform of Mn is basically unchanged.LiCo1/3Mn1/3Fe1/3PO4Relative to LiFePO4Improve voltage platform, increase energy density;Relative to LiMnPO4Improve the electrical conductivity of material, enhance electro-chemical activity phase;Relative to LiCoPO4, improve its cycle performance.Therefore, LiCo1/3Mn1/3Fe1/3PO4It it is a kind of phosphate cathode material with good prospect.Traditional preparation LiCo1/3Mn1/3Fe1/3PO4Method mainly has solid-phase synthesis, spray pyrolysis, coprecipitation, sol-gal process (Electrochem.Commun.11 (2009) 1183;Solid State Ionics178(2008)1676;J.Power Sources242(2013)627;Chem.Mater.22 (2010) 2573.) etc..But all there is the shortcoming that some are intrinsic in these methods, such as: the shortcomings such as synthesis temperature height, synthesis cycle length, control condition harshness, cost height and resulting materials performance are the best, these all limit LiCo1/3Mn1/3Fe1/3PO4Extensive industrialization.It addition, in the research of phosphoric acid positive electrode, carbon cladding is demonstrated to effectively promote the electrochemistry performance of this kind of material.The LiCo with excellent electrochemical performance is prepared it is therefore proposed that a kind of1/3Mn1/3Fe1/3PO4The fast synthesis method of positive electrode.
Summary of the invention
It is an object of the invention to some problems existed for above-mentioned power lithium-ion battery polyanion phosphoric acid salt positive electrode, it is provided that a kind of rapidly and efficiently prepare the ternary polyanion phosphate solid solution LiCo with good electrical chemical property1/3Mn1/3Fe1/3PO4The method of/C positive electrode material.The material particle size prepared by the method is evenly distributed, particle diameter is little, electrical conductivity is high, and has high specific capacity, good cyclical stability, excellent big multiplying power discharging property and high energy density.And the method process is simple, the response time is short, simplifies synthesis technique, reduces preparation cost.
The present invention realizes above-mentioned technical purpose by techniques below means.
The rapid microwave reaction method for preparing of a kind of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode, it is characterised in that comprise the following steps:
(1) be in molar ratio 1~1.1:1/3:1/3:1/3:1 weigh lithium salts, iron salt, manganese salt, cobalt salt, phosphate put into ball grinder;
(2) in ball grinder, add the carbon source of people 7~10wt%, and put into a certain amount of ethanol, be as the criterion raw material can be immersed;
(3) ball grinder is placed on planetary ball mill, with the rotating speed ball millings 5 of 3600 revs/min~10 hours, take out the raw material after grinding, drying, tabletting, it is then placed in being connected with in the atmosphere furnace of noble gas, it is warmed up to 350 DEG C with the heating rate of 5 DEG C/min, at 350 DEG C, decomposes 1~5 hours;
(4) regrinding, tabletting, in microwave reactor under the power of 700W microwave 7~15 minutes, be LiCo after cooling1/3Mn1/3Fe1/3PO4/C。
Preferably, the one during described lithium salts is Quilonorm (SKB), lithium nitrate, lithium carbonate, lithium fluoride.
Preferably, the one during described iron salt is ferric carbonate, ferric oxalate, ferric nitrate.
Preferably, described manganese salt is the one in manganese carbonate, manganese acetate, manganese nitrate.
Preferably, the one during described cobalt salt is cobalt carbonate, cobalt acetate, cobalt nitrate.
Preferably, the one during described phosphate is ammonium dihydrogen phosphate, diammonium phosphate, ammonium phosphate.
Preferably, the one during described carbon source is acetylene black, conductive black super P, porous, electrically conductive carbon black Ketjenblack EC600JD, micropore superconduction carbon black BP2000, carbon nano-fiber (being called for short CNFs), ordered mesopore carbon (being called for short OMC), porous carbon CMK-3, graphene oxide (being called for short GO), Graphene.
Preferably, described noble gas is nitrogen or argon.
Preferably, in described step (3), the pressure of tabletting is 10~15 MPas.
The invention have the advantage that
(1) this invention simplifies synthesis technique, method is simple and convenient, easily controllable, the response time is short, homogeneous heating, low cost.
(2) course of reaction effectively suppresses LiCo1/3Mn1/3Fe1/3PO4Too growing up of crystal grain, even particle size distribution, particle diameter are little, the LiCo of gained1/3Mn1/3Fe1/3PO4/ C composite has special structure, i.e. carbon and is coated on the surface of positive electrode, forms a kind of class nucleocapsid structure electrode material, also has carbon net to be connected between granule simultaneously.Electrical conductivity is high, and has high specific capacity, good cyclical stability, excellent big multiplying power discharging property and high energy density.
(3) by gained LiCo1/3Mn1/3Fe1/3PO4/ C composite is used for lithium ion cell positive, has excellent charge-discharge performance, cycle performance and high rate performance etc..
Accompanying drawing explanation
Fig. 1 is X-ray diffraction analysis (XRD) figure of the embodiment of the present invention 1 sample.
Fig. 2 is scanning electron microscope (SEM) figure of the embodiment of the present invention 1 sample.
Fig. 3 is transmission electron microscope (TEM) figure of the embodiment of the present invention 1 sample.
Fig. 4 is high power transmission electron microscope (HRTEM) figure of the embodiment of the present invention 1 sample.
Fig. 5 is the first charge-discharge curve of the embodiment of the present invention 1 product.
Fig. 6 is the cycle performance curve of the embodiment of the present invention 1 sample.
Fig. 7 is the first charge-discharge curve under 0.1C multiplying power of the embodiment of the present invention 2 sample.
Fig. 8 is the first charge-discharge curve under 0.1C multiplying power of the embodiment of the present invention 3 sample.
Fig. 9 is the first charge-discharge curve under 0.1C multiplying power of the embodiment of the present invention 4 sample.
Figure 10 is the first charge-discharge curve under 0.1C multiplying power of the embodiment of the present invention 5 sample.
Figure 11 is the first charge-discharge curve under 0.1C multiplying power of the embodiment of the present invention 6 sample.
Detailed description of the invention
Below in conjunction with the accompanying drawings and specific embodiment the present invention is further illustrated, but protection scope of the present invention is not limited to this.
Embodiment 1
Ratio for 1.05:1/3:1/3:1/3:1 weighs Quilonorm (SKB), ferric nitrate, cobalt acetate, manganese acetate, diammonium phosphate in molar ratio, put in agate jar or zirconia ball grinding jar, it is subsequently adding the micropore superconduction carbon black BP2000 of about 7~10wt%, add 15~20mL ethanol, be as the criterion raw material can be immersed.Then, ball grinder being placed in ball milling on planetary ball mill, the time is 5~10 hours, and rotating speed is 3600 rpms.After ball milling, dry, 10~15 MPas of lower sheetings, put in the tube furnace being connected with argon, 350 DEG C of heat treatments 1~5 hours.Grind, tabletting, put in microwave reactor, 700W microwave 7~15 minutes, i.e. obtain LiFe1/3Mn1/3Co1/3PO4/ C composite.
Fig. 1 is the X-ray diffraction analysis figure of the product obtained by the present embodiment, shows that product is single orderly LiMPO4Olivine structural, belongs to rhombic system, and space group is Pmnb, does not has any dephasign.Scheming according to the SEM shown in Fig. 2, the particle diameter of available product is at about 250nm;TEM figure shown in Fig. 3 shows and is connected by carbon net between granule;The thickness about 5nm of the HRTEM figure carbon film display carbon film shown in Fig. 4.
Obtained product is assembled into experiment button cell and surveys its charging and discharging capacity and cycle performance, discharge and recharge is carried out under the multiplying power of 0.1C, obtain first charge-discharge curve as shown in Figure 5, charging and discharging curve is made up of three platforms respectively, it is respectively 3.62/3.37 volt, 4.27/3.99 volt and 4.77/4.58 volt, correspond to Fe2+/Fe3+、Mn2+/Mn3+And Co2+/Co3+Electrochemical reaction current potential;First all discharge capacities are 160 MAhs/g.As shown in Figure 6, after being recycled to 30 weeks under 0.1 multiplying power electric current density, capacity remains to stable at about 143 MAhs/g cycle performance.
Embodiment 2
Micropore superconduction carbon black BP2000 in embodiment 1 is replaced with acetylene black, and other are same as in Example 1, and under 0.1 multiplying power electric current density, first all charge/discharge capacity test results are as it is shown in fig. 7, first all charge/discharge capacities are 211/137 MAh/g.
Embodiment 3
Micropore superconduction carbon black BP2000 in embodiment 1 is replaced with conductive black super P, and other are same as in Example 1, and under 0.1 multiplying power electric current density, as shown in Figure 8, first all charge/discharge capacities are 196/145 MAh/g to first all charge/discharge capacity test results.
Embodiment 4
By in embodiment 1, micropore superconduction carbon black BP2000 replaces with porous, electrically conductive carbon black Ketjenblack EC600JD, and other are with embodiment 1, under 0.1 multiplying power electric current density, first all charge/discharge capacity test results are as it is shown in figure 9, first all charge/discharge capacities are 225/147 MAh/g.
Embodiment 5
Quilonorm (SKB), ferric nitrate, cobalt acetate, manganese acetate and diammonium phosphate in embodiment 1 are replaced with lithium carbonate, Ferrox., cobalt carbonate, manganese carbonate and ammonium dihydrogen phosphate respectively, other are with embodiment 1, under 0.1 multiplying power electric current density, as shown in Figure 10, first all charge/discharge capacities are 230/170 MAh/g to first all charge/discharge capacity test results.
Embodiment 6
Quilonorm (SKB), ferric nitrate, cobalt acetate, manganese acetate and diammonium phosphate in embodiment 1 are replaced with lithium carbonate, Ferrox., cobalt carbonate, manganese carbonate and ammonium dihydrogen phosphate respectively, micropore superconduction carbon black (BP2000) replaces with porous, electrically conductive carbon black Ketjenblack EC600JD, other are with embodiment 1, under 0.1 multiplying power electric current density, as shown in figure 11, first all charge/discharge capacities are 216/152 MAh/g to first all charge/discharge capacity test results.
Described embodiment be the present invention preferred embodiment; but the present invention is not limited to above-mentioned embodiment; in the case of without departing substantially from the flesh and blood of the present invention, any conspicuously improved, replacement or modification that those skilled in the art can make belong to protection scope of the present invention.

Claims (5)

1. a rapid microwave reaction method for preparing for power lithium-ion battery ternary polyanion phosphate/carbon positive electrode, It is characterized in that, comprise the following steps:
(1) be in molar ratio 1~1.1:1/3:1/3:1/3:1 weigh lithium salts, iron salt, manganese salt, cobalt salt, phosphate are put into Ball grinder;Described iron salt is the one in ferric carbonate, ferric oxalate, ferric nitrate;
(2) in ball grinder, add the carbon source of people 7~10wt%, and put into a certain amount of ethanol, be as the criterion raw material can be immersed; Described carbon source is acetylene black, conductive black super P, porous, electrically conductive carbon black Ketjenblack EC600JD, micropore superconduction carbon black BP2000, carbon nano-fiber (being called for short CNFs), ordered mesopore carbon (being called for short OMC), porous carbon CMK-3, oxidation stone One in ink alkene (being called for short GO), Graphene;
(3) ball grinder is placed on planetary ball mill, with the rotating speed ball millings 5 of 3600 revs/min~10 hours, takes out after grinding Raw material, drying, tabletting, be then placed in being connected with in the atmosphere furnace of noble gas, be warmed up to 350 DEG C with the heating rate of 5 DEG C/min, 1~5 hours is decomposed at 350 DEG C;Described noble gas is nitrogen or argon;The pressure of tabletting is 10~15 MPas;
(4) regrinding, tabletting, in microwave reactor under the power of 700W microwave 7~15 minutes, be after cooling LiCo1/3Mn1/3Fe1/3PO4/C。
Preparation method the most according to claim 1, it is characterised in that described lithium salts be Quilonorm (SKB), lithium nitrate, lithium carbonate, One in lithium fluoride.
Preparation method the most according to claim 1, it is characterised in that described manganese salt is manganese carbonate, manganese acetate, manganese nitrate In one.
Preparation method the most according to claim 1, it is characterised in that described cobalt salt is cobalt carbonate, cobalt acetate, cobalt nitrate In one.
Preparation method the most according to claim 1, it is characterised in that described phosphate is ammonium dihydrogen phosphate, phosphoric acid hydrogen two One in ammonium, ammonium phosphate.
CN201410192405.XA 2014-05-08 2014-05-08 A kind of rapid microwave reaction method for preparing of power lithium-ion battery ternary polyanion phosphate/carbon positive electrode Active CN103996823B (en)

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CN106935849B (en) * 2015-12-31 2019-12-20 比亚迪股份有限公司 Lithium ion battery anode material and preparation method thereof
CN106532007B (en) * 2016-12-19 2020-10-09 高霞 Preparation method of lithium ion secondary battery anode for electric toothbrush or electric shaver
CN107742713A (en) * 2017-10-27 2018-02-27 天津先众新能源科技股份有限公司 A kind of synthetic method of graphene/lithium ferric manganese phosphate material
CN109103444A (en) * 2018-08-30 2018-12-28 上海力信能源科技有限责任公司 A kind of LiMPO4The preparation method of In-situ reaction graphene
CN111668448B (en) * 2020-07-14 2023-02-24 贵州梅岭电源有限公司 Lithium iron phosphate modified composite material and preparation method thereof

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CN1911792A (en) * 2006-08-22 2007-02-14 南京大学 Microwave synthesis method for carbon coated iron phosphate of ion battery composite anode material
CN100513305C (en) * 2006-12-21 2009-07-15 四川师范大学 Polycrystalline LiFePO4 powder solid phase-microwave synthesis method
KR101135700B1 (en) * 2010-01-21 2012-04-13 한국과학기술원 Method for manufacturing a metal oxalate material
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