CN103500818B - The two component surface modification ferric fluoride anode materials of a kind of Aluminate doping phosphoric acid titanium lithium and preparation method - Google Patents
The two component surface modification ferric fluoride anode materials of a kind of Aluminate doping phosphoric acid titanium lithium and preparation method Download PDFInfo
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- H—ELECTRICITY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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Abstract
The two component surface modification ferric fluoride anode materials of a kind of Aluminate doping phosphoric acid titanium lithium and preparation method, is characterized in that the titanium phosphate lithium Li of Aluminate and silicon, aluminium doping1.3Al0.1Ti1.9Si0.2P2.8O12In high energy ball mill, after ball milling heat treatment after a while, obtain FeF with synthesis material3Positive electrode. FeF3Middle fluorine has lone pair electrons, forms coordination and combination with aluminium ion strong effect in Aluminate, and the reactive group of Aluminate is active strong simultaneously, is hydroxyl and Li by alkoxyl fast hydrolyzing1.3Al0.1Ti1.9Si0.2P2.8O12In conjunction with and simultaneously and FeF3Positive electrode surface hydroxyl polycondensation combination, therefore by the effect of Aluminate, by doping phosphoric acid titanium lithium Li1.3Al0.1Ti1.9Si0.2P2.8O12Be bonded to FeF3Anodal particle surface, makes both particles form good contact, and Li1.3Al0.1Ti1.9Si0.2P2.8O12Be lithium ion good conductor, its ionic conductivity is 10 of cobalt acid lithium3-104Doubly. Therefore can overcome FeF3The shortcoming that positive electrode ionic conductivity is extremely low, improves FeF3The chemical property of material.
Description
Technical field
The present invention relates to a kind of high power capacity ferric flouride lithium electricity positive electrode manufacture method technical field.
Background technology
Lithium rechargeable battery have volume, weight energy than high, voltage is high, self-discharge rate is low, memory-less effect, circulation longevityLife is long, the high absolute advantage of power density, has at present to exceed 30,000,000,000 dollars of/year shares and to surpass in global portable power source market10% the speed crossed increases gradually. Particularly in recent years, along with petering out of fossil energy, solar energy, wind energy, biologyThe new forms of energy such as mass-energy become the alternative of traditional energy gradually, and wherein wind energy, solar energy have intermittence, continue for meetingSupply of electric power need to use a large amount of energy-storage batteries simultaneously; The urban air-quality problem that vehicle exhaust brings is day by day serious,Instant stage has been arrived in vigorously advocating and developing of electric motor car (EV) or hybrid electric vehicle (HEV); These demands provideLithium ion battery explosive growth point, also the performance of lithium ion battery is had higher requirement simultaneously.
The raising of the capacity of anode material for lithium-ion batteries is the primary goal that scientific and technical personnel study, the research and development of high power capacity positive electrodeCan alleviate that current lithium ion battery group volume is large, heavy weight, price high-leveled and difficult with meet high power consumption and high-power equipment needs inningsFace. But since lithium ion battery commercialization in 1991, the actual specific capacity of positive electrode is hovered all the time at 100-180mAh/gBetween, the low bottleneck that promotes lithium ion battery specific energy that become of positive electrode specific capacity. At present commercial lithium ion batteryFor practical widely positive electrode is LiCoO2, the theoretical specific capacity of cobalt acid lithium is 274mAh/g, and actual specific capacity existsBetween 130-140mAh/g, and cobalt is strategic materials, expensive and have larger toxicity. Therefore countries in the world in recent years,Researcher be devoted to the research and development of Olivine-type Cathode Material in Li-ion Batteries always, up till now, the lithium-ion electric filtering outPond positive pole reaches tens of kinds, but really has potential commercial applications prospect or appeared at positive electrode on market really veryLack. As lithium manganate having spinel structure LiMn2O4, its cost is lower, and than being easier to preparation, security performance is also relatively good, butCapacity is lower, and theoretical capacity is 148mAh/g, and actual capacity is at 100-120mAh/g, and this material capacity circulation keeps energyPower is not good, and under high temperature, capacity attenuation is very fast, Mn3+John-Teller effect and the dissolving in electrolyte perplexing and grinding for a long timeStudy carefully personnel. The LiNiO of layer structure2And LiMnO2Although have larger theoretical specific capacity, be respectively 275mAh/g and 285MAh/g, but their preparations are very difficult, poor heat stability, cyclicity is very poor, and capacity attenuation is very fast. And at present byWalk business-like LiFePO4 LiFePO4Cost is low, Heat stability is good, environmental friendliness, but its theoretical capacity approximately only has 170MAh/g, and actual capacity in about 140mAh/g [ChunSY, BlokingJT, ChiangYM, NatureMaterials,2002,1:123-128.]. There is at present the positive electrode that exceedes 200mAh/g specific capacity of market prospects to only have lithium vanadate Li1+xV3O8，Li1+xV3O8Material can have and has the capacity that even approaches 300mAh/g, but its electric discharge average voltage is lower and also production process in vanadiumOxide often toxicity is larger. High lithium is than on positive electrode in recent years, particularly manganese base manganese-nickel binary and manganese base manganese-nickel-cobalt ternaryThe high lithium of system solid solution is than positive electrode, have exceed the Capacity Ratio of 200mAh/g, higher heat endurance with respect to cheap becomingThis and receive people's concern, but performance under this material high magnification is very undesirable, limited its in electrokinetic cell shouldWith [Young-SikHong, YongJoonPark, etal., SolidStateIonics, 2005,176:1035-1042].
In recent years, FeF3Material is because its capacity is high, the low visual field that enters researcher of the prices of raw and semifnished materials. FeF3Material and biographyThe operation principle of system anode material for lithium-ion batteries is different, and traditional lithium ion cell positive and negative pole all exist the lithium ion canTo embed or the space of deintercalation, and lithium ion in electrolyte between positive pole and negative pole back and forth embedding and deintercalation and discharge as" rocking chair " battery that Armand etc. propose. And FeF3A kind of transition material, namely in whole discharge process,FeF3There is following variation [BadwayF, CosandeyF, PereiraN, etal., ElectrodesforLiBatteries, J.Electrochem.Soc.，2003，150(10)：A1318-A1327.]：
Li++FeF3+e→LiFeF3----(1)
LiFeF3+2Li++2e→3LiF+Fe-(2)
The first step and the namely lithium ion embedding of traditional lithium ion, in whole course of reaction, lattice does not have large variation; And secondPortion is the displacement reaction of metal, and conversion has occurred parent lattice completely. The theoretical capacity of the first step is 237mAh.g-1; Completely anti-Should be able to realize the conversion of 3 electronics, the theoretical capacity of second stage is 474mAh.g-1; Total capacity is 711mAh.g-1; AlthoughThis material does not have clear and definite discharge platform, and average discharge volt is also lower, but it approaches 800mAh.g-1Theoretical specific capacity alsoIt is the attention that has obtained investigation of materials personnel height. But, pass through as Arai, Amatucci[BadwayF, PereiraN,CosandeyF, etal., J.Electrochem.Soc., 2003,150 (9): A1209-A1218.] etc. scholar's research find, be by itIt not is an easy thing that theoretical capacity major part discharges. First FeF3The non-constant of electronic conduction ability, simultaneously itsLithium ion conductivity is also very low, and product LiF after conversion is electronic body, and simultaneously the ability of conductive lithium ion is also very poor,Thereby cause FeF3The available capacity that material can utilize is lower, can only discharge in early days about 50-100mAh.g in research-1CanContrary capacity; Charging and discharging currents is little, and multiplying power property is poor; Polarization in charge and discharge process is comparatively serious, charging/discharging voltage platform gapVery large; Capacitance reserve ability is not good, and along with discharging and recharging the increase of number of times, capacity attenuation is serious. Afterwards Amatucci etc. by withMaterial with carbon element forms carbon/ferric flouride nano-complex (CMFNCs) through long-time high-energy ball milling and has improved its conductive capability, greatly carriesHigh its chemical property, its discharge capacity can reach 200mAh.g-1Left and right [BadwayF, MansourA.N, PereiraN,Etal., Chem.Mater., 2007,19 (17): 4129-4141.]. Secondly, the capacity that this material is higher need to be in higher temperature(50-70 DEG C) just can discharge, and main cause is that the activation energy of conversion reaction of second stage is very high, needs higher temperature gramTake this activation energy and have reaction speed faster, the charging platform of this material and the voltage difference of discharge platform are very high in addition, are alsoReaction activity is high, the not good embodiment of reaction invertibity. Finally, because FeF3Material is slightly soluble in cold water, so conventionally adopt secondThe method preparation of alcohol liquid phase needs to use a large amount of ethanol in building-up process, and economy is not good. Be unsuitable in industrial applications.
Therefore, improve FeF3What the chemical property of positive electrode was primary is to seek a kind of electronic conductance that can simultaneously improve materialThe method of rate and lithium ion conductivity makes that preparation flow is simple as far as possible, cost is low, convenient and swift simultaneously, and this is to FeF3JustThe development and application of utmost point material is particularly important.
Summary of the invention
The present invention is directed to existing background technology and proposed the two component surface modification ferric fluoride anode materials of a kind of Aluminate doping phosphoric acid titanium lithiumMaterial and preparation method. The method is by the titanium phosphate lithium Li of Aluminate and silicon, aluminium doping1.3Al0.1Ti1.9Si0.2P2.8O12With synthesis materialIn high energy ball mill, after ball milling heat treatment after a while, obtain FeF3Positive electrode. FeF3Middle fluorine has lonely to electricitySon, forms coordination and combination with aluminium ion strong effect in Aluminate, and the reactive group of Aluminate is active strong simultaneously, passes through alcoxylBase fast hydrolyzing is hydroxyl and Li1.3Al0.1Ti1.9Si0.2P2.8O12In conjunction with and simultaneously and FeF3Positive electrode surface hydroxyl polycondensation combination,Therefore by the effect of Aluminate, by doping phosphoric acid titanium lithium Li1.3Al0.1Ti1.9Si0.2P2.8O12Be bonded to FeF3Anodal particle surface,Make both particles form good contact, and Li1.3Al0.1Ti1.9Si0.2P2.8O12Be lithium ion good conductor, its ionic conductivity is10 of cobalt acid lithium3-104Doubly. Therefore can overcome FeF3The shortcoming that positive electrode ionic conductivity is extremely low, improves FeF3MaterialChemical property.
The preparation method of the two component surface modification ferric fluoride anode materials of this Aluminate doping phosphoric acid titanium lithium, it is characterized in that byAl2O3：SiO2：TiO2：NH4H2PO4：Li2CO3Evenly mix for the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio), add95% ethanol of 3%-9%, in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min, after ball milling finishes60 DEG C-80 DEG C, in the vacuum drying oven that pressure is 10Pa-100Pa, be dried 2-10 hours, after taking-up, grind in alms bowl and again grind at agate10-30 minute, the powder after grinding is warmed up to 600-1000 DEG C of insulation with the speed of 5-30 DEG C/min and makes for 5-16 hourLi1.3Al0.1Ti1.9Si0.2P2.8O12Solid electrolyte powder. Will be containing crystallization water molysite and ammonium fluoride (mol ratio is 1.0:3.0-3.6) and heavyThe Li that amount percentage is 3-15%1.3Al0.1Ti1.9Si0.2P2.8O12The auxiliary agent that solid electrolyte powder, percentage by weight are 0.5-3.0%And the percentage by weight Aluminate that is 0.5-3.0% normal temperature ball milling after 5-20 hour under atmosphere protection in high energy ball mill, extractMaterial is warmed up to 300-450 degree constant temperature cooling after 2-10 hours under 5% hydrogen and 95% argon gas mixed gas protected, preparesObtain FeF3Positive electrode.
Above-mentioned is Fe (NO containing crystallization water molysite3)3·9H2O，FeCl3·6H2O and Fe2(SO4)3·9H2One in O;
Above-mentioned Aluminate is the one in distearyl acyl-oxygen aluminum isopropoxide acid esters, isopropyl two oleic acid acyloxy Aluminates.
Above-mentioned auxiliary agent is Tween-80, the one in span-60 and tx-10;
Above-mentioned atmosphere is high pure nitrogen or high-purity argon gas;
Fig. 1 is charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material, voltage range 2.0V-4.0V,Charging and discharging currents 0.1C.
Compared with prior art, the invention has the advantages that: FeF3Middle fluorine has lone pair electrons, strong with aluminium ion in AluminateEffect forms coordination and combination, and the reactive group of Aluminate is active strong simultaneously, by alkoxyl fast hydrolyzing be hydroxyl withLi1.3Al0.1Ti1.9Si0.2P2.8O12In conjunction with and simultaneously and FeF3Positive electrode surface hydroxyl polycondensation combination, therefore by the work of AluminateWith, by doping phosphoric acid titanium lithium Li1.3Al0.1Ti1.9Si0.2P2.8O12Be bonded to FeF3Anodal particle surface, makes both particles form goodGood contact, and Li1.3Al0.1Ti1.9Si0.2P2.8O12Be lithium ion good conductor, its ionic conductivity is 10 of cobalt acid lithium3-104Doubly.Therefore can overcome FeF3The shortcoming that positive electrode ionic conductivity is extremely low, improves FeF3The chemical property of material.
Brief description of the drawings
Charging capacity, discharge capacity and the efficiency for charge-discharge figure of front 10 circulations of this material of Fig. 1, voltage range 2.0V-4.0V,Charging and discharging currents 0.1C.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
Embodiment 1: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 3.5% 95% ethanol, in ball mill with the rotating speed ball milling of 110 revs/min 12 hours, ball milling knotIn the vacuum drying oven that is 15Pa at 65 DEG C of pressure after bundle, be dried 2.5 hours, after taking-up, grind in alms bowl and again grind 15 minutes at agate,Powder after grinding is warmed up to 650 DEG C of insulations with the speed of 6 DEG C/min and within 6 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. By Fe (NO3)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.1) and percentage by weight are 3.2%1.3Al0.1Ti1.9Si0.2P2.8O12The distearyl that the Tween-80 that solid electrolyte powder, percentage by weight are 0.6% and percentage by weight are 0.6%Under high pure nitrogen protection, normal temperature ball milling is after 5 hours in high energy ball mill for oxygen isopropoxy Aluminate, and taking-up material, at 5% hydrogenWith to be warmed up to 300 degree constant temperature under 95% argon gas mixed gas protected cooling after 2 hours, prepare FeF3Positive electrode.
Embodiment 2: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 8% 95% ethanol, and in ball mill, with the rotating speed ball milling of 450 revs/min 45 hours, ball milling finishedAfter in the vacuum drying oven that is 80Pa at 75 DEG C of pressure dry 8 hours, after taking-up, grind in alms bowl and again grind 25 minutes at agate, grindPowder after mill is warmed up to 900 DEG C of insulations with the speed of 25 DEG C/min and within 15 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. By FeCl3·6H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.6) and percentage by weight are 13%1.3Al0.1Ti1.9Si0.2P2.8O12The isopropyl two that the span-60 that solid electrolyte powder, percentage by weight are 2.8% and percentage by weight are 3.0%Under high-purity argon gas protection, normal temperature ball milling is after 20 hours in high energy ball mill for oleic acid acyloxy Aluminate, and taking-up material, at 5% hydrogenUnder gas and 95% argon gas mixed gas protected, be warmed up to 450 degree constant temperature cooling after 9 hours, prepare FeF3Positive electrode.
Embodiment 3: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 5% 95% ethanol, and in ball mill, with the rotating speed ball milling of 200 revs/min 25 hours, ball milling finishedAfter in the vacuum drying oven that is 60Pa at 70 DEG C of pressure dry 7 hours, after taking-up, grind in alms bowl and again grind 20 minutes at agate, grindPowder after mill is warmed up to 750 DEG C of insulations with the speed of 20 DEG C/min and within 12 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. By Fe2(SO4)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.5) and percentage by weight are 7%1.3Al0.1Ti1.9Si0.2P2.8O12The distearyl acyl-oxygen that the tx-10 that solid electrolyte powder, percentage by weight are 2.0% and percentage by weight are 2.1%Under high pure nitrogen protection, normal temperature ball milling is after 15 hours in high energy ball mill for isopropoxy Aluminate, and taking-up material, at 5% hydrogenWith to be warmed up to 400 degree constant temperature under 95% argon gas mixed gas protected cooling after 8 hours, prepare FeF3Positive electrode.
Embodiment 4: by Al2O3：SiO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 4% 95% ethanol, and in ball mill, with the rotating speed ball milling of 400 revs/min 50 hours, ball milling finishedAfter in the vacuum drying oven that is 90Pa at 80 DEG C of pressure dry 5 hours, after taking-up, grind in alms bowl and again grind 20 minutes at agate, grindPowder after mill is warmed up to 600 DEG C of insulations with the speed of 25 DEG C/min and within 12 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. By Fe (NO3)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.2) and percentage by weight are 10%1.3Al0.1Ti1.9Si0.2P2.8O12Isopropyl two oil that the tx-10 that solid electrolyte powder, percentage by weight are 2.5% and percentage by weight are 1.0%Under high-purity argon gas protection, normal temperature ball milling is after 10 hours in high energy ball mill for acid acyloxy Aluminate, and taking-up material, at 5% hydrogenWith to be warmed up to 300 degree constant temperature under 95% argon gas mixed gas protected cooling after 7 hours, prepare FeF3Positive electrode.
Embodiment 5: by Al2O3：8iO2：TiO2：NH4H2PO4：Li2CO3For the ratio of 0.05:0.2:1.9:2.8:0.65 (mol ratio)Example is evenly mixed, and adds 5% 95% ethanol, and in ball mill, with the rotating speed ball milling of 250 revs/min 30 hours, ball milling finishedAfter in the vacuum drying oven that is 90Pa at 70 DEG C of pressure dry 8 hours, after taking-up, grind in alms bowl and again grind 10 minutes at agate, grindPowder after mill is warmed up to 700 DEG C of insulations with the speed of 5 DEG C/min and within 16 hours, makes Li1.3Al0.1Ti1.9Si0.2P2.8O12Solid-state electricitySeparate matter powder. By Fe2(SO4)3·9H2The Li that O and ammonium fluoride (mol ratio is 1.0:3.3) and percentage by weight are 12%1.3Al0.1Ti1.9Si0.2P2.8O12Isopropyl two oil that the tx-10 that solid electrolyte powder, percentage by weight are 1.5% and percentage by weight are 1.0%Under high pure nitrogen protection, normal temperature ball milling is after 15 hours in high energy ball mill for acid acyloxy Aluminate, and taking-up material, at 5% hydrogenWith to be warmed up to 300 degree constant temperature under 95% argon gas mixed gas protected cooling after 8 hours, prepare FeF3Positive electrode.
Claims (5)
1. a preparation method for the two component surface modification ferric fluoride anode materials of Aluminate doping phosphoric acid titanium lithium, it is characterized in that byAl2O3∶SiO2∶TiO2∶NH4H2PO4∶Li2CO3Taking mol ratio as 0.05: 0.2: 1.9: the ratio of 2.8: 0.65 is evenly mixed, and adds95% ethanol of 3%-9%, in ball mill with the rotating speed ball milling 10-50 hour of 100-500 rev/min, after ball milling finishes60 DEG C-80 DEG C, in the vacuum drying oven that pressure is 10Pa-100Pa, dry 2-10 hour, grinds in alms bowl and again grinds at agate after taking-up10-30 minute, the powder after grinding is warmed up to 600-1000 DEG C of insulation with the speed of 5-30 DEG C/min and makes for 5-16 hourLi1.3Al0.1Ti1.9Si0.2P2.8O12Solid electrolyte powder; Be 1.0 by mol ratio: 3.0-3.6 containing crystallization water molysite and ammonium fluoride andPercentage by weight is the Li of 3-15%1.3Al0.1Ti1.9Si0.2P2.8O12What solid electrolyte powder, percentage by weight were 0.5-3.0% helpsAgent and percentage by weight be the Aluminate of 0.5-3.0% in high energy ball mill under atmosphere protection normal temperature ball milling after 5-20 hour, take outMaterial is warmed up to 300-450 degree constant temperature cooling after 2-10 hour under 5% hydrogen and 95% argon gas mixed gas protected, systemThe standby FeF that obtains3Positive electrode.
2. preparation method according to claim 1, is characterized in that above-mentioned is Fe (NO containing crystallization water molysite3)3·9H2O，FeCl3·6H2O and Fe2(SO4)3·9H2One in O.
3. preparation method according to claim 1, it is characterized in that above-mentioned Aluminate be distearyl acyl-oxygen aluminum isopropoxide acid esters,One in isopropyl two oleic acid acyloxy Aluminates.
4. preparation method according to claim 1, is characterized in that above-mentioned auxiliary agent is Tween-80, in span-60 and tx-10One.
5. preparation method according to claim 1, is characterized in that above-mentioned atmosphere is high pure nitrogen or high-purity argon gas.
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| CN102468486A (en) * | 2010-11-02 | 2012-05-23 | 三星Sdi株式会社 | Positive active material for lithium secondary battery and method of manufacturing same |
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| CN1458704A (en) * | 2002-05-13 | 2003-11-26 | 三星Sdi株式会社 | Process for preparing battery active matter and battery active matter prepared therefrom |
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| J. Xie et al..Amorphous LiCoO2 thin fi * |
| lms on Li1+x+yAlxTi2−xSiyP3−yO12 prepared by radio frequency magnetron sputtering for all-solid-state Li-ion batteries..《Electrochimica Acta》.2010,第55卷第5440-5445页. * |
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