CN103094576A - Nickel-based positive electrode material, and preparation method thereof and battery - Google Patents

Nickel-based positive electrode material, and preparation method thereof and battery Download PDF

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CN103094576A
CN103094576A CN2011103384141A CN201110338414A CN103094576A CN 103094576 A CN103094576 A CN 103094576A CN 2011103384141 A CN2011103384141 A CN 2011103384141A CN 201110338414 A CN201110338414 A CN 201110338414A CN 103094576 A CN103094576 A CN 103094576A
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nickel
carbonate
base anode
lithium
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CN103094576B (en
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卢世刚
孙学义
庄卫东
张向军
张超
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GUOLIAN AUTOMOBILE POWER CELL INSTITUTE CO., LTD.
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Beijing General Research Institute for Non Ferrous Metals
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    • 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 relates to a nickel-based positive electrode material, and a preparation method thereof and a battery. The composition of the nickel-based positive electrode material is LiaNibCocMndMeM'fO2-g/2Fg (M is at least one selected from Ti, Zr, Al, Fe, Cr, Si, and Cu; M' is at least one selected from Mg, Ca, Sr, Ba, and W; a is no smaller than 0.95 and no greater than 1.2; b is no smaller than 0.2 and no greater than 0.9; c is no smaller than 0 and no greater than 0.4; d is no smaller than 0 and no greater than 0.4; e+f is greater than 0.05and no greater than 0.2; and g is greater than 0.02 and no greater than 0. 1). Anions and cations are used in co-doping. With a synergistic effect, nickel-based positive electrode material capacity, structural stability and circulation performance are greatly improved. The preparation method at least comprises the 4 steps that: (1) corresponding raw materials are weighed according to the molar ratio consistent with LiaNibCocMndMeM'fO2-g/2Fg; (2) the raw materials are subjected to wet grinding; (3) slurry obtained by grinding is dried; and (4) the dried material is subjected to solid-phase synthesis under a temperature of 500-1100 DEG C. With the process, the raw materials can be more uniformly dispersed, and the obtained product has the advantages of high capacity and good circulation performance. The process is simple, and has the advantages of low cost and suitability for large-scale industrialized productions. With the process, problems such as complicated process and acid and alkali pollution of a wet chemical precursor preparation method are avoided. The invention also relates to a battery with the material as an active substance.

Description

A kind of nickel-base anode material and preparation method thereof and battery
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof and battery, belong to the energy and material technical field.
Background technology
1999, LiNi 1-x-yCo xMn yO 2(0<x<0.5,0<y<0.5) (nickel-base anode material) by reported first, and this material has significantly improved the capacity of material by introducing nickel ion, reduce lithium-nickel cation mixing, the fail safe that improves material by introducing manganese ion by introducing cobalt ions.This material combines LiCoO 2, LiNiO 2, LiMnO 2The advantage of three class materials is considered to best and can replaces LiCoO 2One of positive electrode.But in this material, the radius of lithium ion and bivalent nickel ion approaches, and mixing easily occurs, and makes the structural stability variation, thus also variation of the cycle performance of material.In order to suppress this mixing phenomenon, usually adopt cation or (with) anion doped structural stability, thermal stability and the high rate performance etc. that improve this material.
Synthesizing of nickel-base anode material adopted liquid-phase coprecipitation and high temperature solid-state method mostly at present.Liquid-phase coprecipitation is first the aqueous solution of nickel salt, cobalt salt, manganese salt and lithium hydroxide, NaOH or sodium carbonate co-precipitation to be generated hydroxide or carbonate precursor, then this presoma is synthesized with at high temperature roasting after lithium salts mixes.Lv Xiangyang etc. (CN101269849A) first adopt special depositing technology to prepare a kind of high density spherical nickel-cobalt manganese presoma, then with this presoma and the lithium source mixed after roasting under given conditions, obtained at last the high density nickle cobalt lithium manganate.The method can evenly be mixed on atomic level by three kinds of transition metals, but complex process, poor repeatability.The high temperature solid-state rule is with direct synthetic product at high temperature after the compound of nickel, cobalt, manganese and lithium ground and mixed together.The people such as Liao Qinlin (CN1610153A) are take oxide, hydroxide or the carbonate of nickel, lithium, cobalt as raw material, add wherein a kind of element of Ti, Mg, Cr, Mn, mix in ball mill, under the 600-800 degree pre-burning 5-15 hour, then synthesized 5-20 hour under the 700-900 degree, obtain end product after pulverizing, ball milling, classification.The people such as K.W.Eberman (US7211237B2) have improved solid phase method, to contain cobalt, contain manganese, oxide or oxide precursor nickeliferous and that contain lithium carry out wet-milling, the fine particle slurry material that contains cobalt, manganese, nickel and the lithium of abundant dispersion with formation, then slurry is heated to form have single-phase lithium transition metal compound.Above-mentioned two kinds of methods are simple, but are difficult to obtain the pattern of homogeneous.The Zhi mound is virtuous controls (CN101093887A) provides a kind of method for preparing the layered lithium-nickel-based compound oxide powder of high density lithium secondary battery positive electrode material, first will contain nickel compound, can partly replace the metallic element compound pulp spray drying of nickel, then with the compound of lithium, then prepare the layered lithium-nickel-based compound oxide powder of positive electrode material of lithium secondary cell by baking.This kind method is simple, and pattern is easily controlled, and easily again causes the element uneven distribution but be dry mixed.
Summary of the invention
The main technical problem to be solved in the present invention is: for the problems referred to above of nickel-base anode material, provide a kind of anode material for lithium-ion batteries and preparation method thereof and battery.Improve capacity and the stability of material by anion and cation co-doped.The oxygen that replaces part by the anion fluorine can be so that material has stable cycle performance under high cut-ff voltage, better high rate performance and thermal stability.The replacement of fluorine ion can also promote the growth of primary particle, thereby obtains higher tap density.And by at least a replacement part Mn in Mg, Ca, Sr, Ba, W, because these elements self are not participated in reaction, so in the situation that do not affect the stability that the capacity of material can also improve material structure.Discharge capacity not only can be improved by at least a doping the in Ti, Zr, Al, Fe, Cr, Si, Cu, the decomposition of active material can also be suppressed.
The chemical formula of nickel-base anode material of the present invention is Li aNi bCo cMn dM eM’ fO 2-g/2F g, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05<e+f≤0.2,0.02<g≤0.1.
Preferred 0.05<e+f≤0.1,0.02<g≤0.05.
Preferred M is: at least a in Ti, Zr, Al, Fe, Si, M ' is: at least a in Mg, Ca, W.
Nickel-base anode material of the present invention is a kind of in following composition:
LiNi 0.5Co 0.28Mn 0.16Si 0.03Zr 0.03O 1.98F 0.04
LiNi 0.58Co 0.18Mn 0.18Si 0.03Zr 0.03O 1.98F 0.04
LiNi 0.68Co 0.13Mn 0.13Si 0.03Zr 0.03O 1.98F 0.04
LiNi 0.78Co 0.08Mn 0.08Si 0.03Zr 0.03O 1.98F 0.04
LiNi 0.68Co 0.13Mn 0.11Al 0.05Zr 0.03O 1.98F 0.04
LiNi 0.5Co 0.28Mn 0.15Al 0.04Zr 0.03O 1.98F 0.04、LiNi 0.86Co 0.08Al 0.03Mg 0.03O 1.975F 0.05
LiNi 0.58Co 0.18Mn 0.18Al 0.03Mg 0.03O 19.8F 0.04
Li 0.98Ni 0.78Co 0.16Si 0.02Al 0.02Mg 0.03O 1.975F 0.05
Li 1.04Ni 0.76Co 0.16Al 0.03Mg 0.03O 1.985F 0.03
LiNi 1/3Co 1/3Mn 1/3-0.06Al 0.04Mg 0.02O 1.985F 0.03
The present invention proposes simultaneously this nickel-base anode material preparation method of preparation, the method comprises following processing step at least:
1) respectively with lithium source, manganese source, cobalt source, nickel source, and be selected from Ti source, Zr source, Al source, Fe source, Cr source, Si source, Cu source at least a, and be selected from least a in Mg source, Ca source, Sr source, Ba source, W source and the F source as raw material, press chemical formula Li aNi bCo cMn dM eM’ fO 2-g/2F gA mole proportioning take corresponding raw material, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05<e+f≤0.2,0.02<g≤0.1;
2) add appropriate liquid to carry out wet-milling in raw material;
3) with the slurry drying after wet-milling;
4) at high temperature carry out roasting after drying and synthesize, the roasting synthesis temperature is 500-1100 ℃.
A kind of nickel-base anode material preparation method of the present invention, described lithium source be anhydrous lithium hydroxide, it is at least a to contain in crystallization water lithium hydroxide, lithium carbonate, preferred lithium carbonate.
A kind of nickel-base anode material preparation method of the present invention, described manganese source are at least a in manganese metal, manganese monoxide, manganese dioxide, manganese carbonate, and be at least a in preferable alloy manganese, manganese carbonate.
A kind of nickel-base anode material preparation method of the present invention, described cobalt source are at least a in cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, cobalt hydroxide, cobalt carbonate, are preferably in cobalt sesquioxide, cobaltosic oxide at least a.
A kind of nickel-base anode material preparation method of the present invention, described nickel source are at least a in nickel sesquioxide, nickel protoxide, nickel hydroxide, nickelous carbonate, are preferably in nickel sesquioxide or nickel protoxide at least a.
a kind of nickel-base anode material preparation method of the present invention, described titanium source is titanium dioxide, described zirconium source is zirconia, described aluminium source is metallic aluminium, alundum (Al2O3), at least a in aluminium hydroxide, described source of iron is iron oxide, ferrous oxide, iron hydroxide, at least a in ferrous hydroxide, described chromium source is crome metal, chrome green, at least a in chromium hydroxide, described silicon source is silicon dioxide, described copper source is cupric oxide, cuprous oxide, at least a in copper carbonate, described magnesium source is magnesium carbonate, at least a in magnesium oxide, described calcium source is calcium carbonate, calcium oxide, at least a in calcium hydroxide, described strontium source is strontium carbonate, at least a in strontium oxide strontia, described barium source is brium carbonate, described tungsten source is tungstic acid, described fluorine source is lithium fluoride.
A kind of nickel-base anode material preparation method of the present invention, described step 2) wet-milling in comprises in pre-grinding, corase grind, fine grinding two kinds at least.Pre-grinding is to make slurry particle diameter (D 50) less than 3 microns; Corase grind is to make slurry particle diameter (D 50) less than 1 micron; Fine grinding is to make slurry particle diameter (D 50) less than 0.1 micron.
In described step 2) in, pre-time consuming was for 2-30 hour.
In described step 2) in, the corase grind time is 2-5 hour.
In described step 2) in, the fine grinding time is 2-5 hour.
A kind of nickel-base anode material preparation method of the present invention, described step 3) grain diameter (D of gained powder after dry in 50) less than 1 micron.
In described step 3) in, dry temperature is 80-250 ℃.
A kind of nickel-base anode material preparation method of the present invention, the synthetic temperature of described roasting is preferred 800-1000 ℃, most preferably is 800-900 ℃.
In described step 4) in, roasting time is 5-40 hour.
A kind of positive pole of the present invention will mix with conductive agent and bonding agent by the nickel-base anode material that above-mentioned composition and preparation method obtain, and the mixture that obtains is coated in the positive pole that supports formation lithium ion battery on conducting base.
A kind of battery of the present invention, negative pole, barrier film, electrolyte that above-mentioned positive pole is compatible with electricity are placed in container and form lithium ion battery.
Advantage of the present invention is:
(1) realize anion and cation co-doped in the nickel-base anode material, by synergy, capacity, structural stability and the cycle performance of nickel-base anode material all are improved.
(2) adopt respectively the different model ball mill to carry out the pre-grinding in pre-grinding, corase grind, fine grinding, two kinds of combinations of corase grind according to the particle diameter distribution of raw material and the features such as hardness of material, or two kinds of combinations of pre-grinding, fine grinding, or the combination of two kinds of corase grind, fine grinding, or the combination of three kinds of pre-grinding, corase grind, fine grinding; Fully the advantage with ball millings at different levels is used, and not only increases work efficiency, and raw material is disperseed more even, and particle diameter is more tiny.The tiny motive force that can increase sintering of particle has shortened the diffusion length of atom, accelerates sintering process, and can reduce sintering temperature.The method all adds raw material is disposable, need not to add any raw material in the subsequent technique process, has avoided secondary ball milling mixing (secondary ball milling mixes and refers to again add after raw material mixing and ball milling again) again to cause the element skewness.The method adopts solid phase method synthetic, and technical process is simple, and cost is low, is easy to large industrial production, has avoided wet chemistry method to prepare the flow process of presoma complexity and the pollution problem of soda acid.
Description of drawings
The FE-SEM picture of the nickel-base anode material that Fig. 1 the present invention synthesizes (embodiment 7).
The X ray diffracting spectrum of the nickel-base anode material that Fig. 2 the present invention synthesizes (embodiment 7).
The first charge-discharge curve of the nickel-base anode material that Fig. 3 the present invention synthesizes (embodiment 7).
The cycle performance of the nickel-base anode material that Fig. 4 the present invention synthesizes (embodiment 7).
Embodiment
Below with embodiment, technical scheme of the present invention is further described; to help product of the present invention and manufacture method are done further to understand; protection scope of the present invention is not subjected to the restriction of these embodiment, and protection scope of the present invention is decided by claims.
Specific embodiment 1:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 0.5Co 0.28Mn 0.16Si 0.03Zr 0.03O 1.98F 0.04363.2g lithium carbonate, 10.6g lithium fluoride, 382.1g nickel protoxide, 230.0g cobaltosic oxide, 32.9g zirconia, 18.4g silicon dioxide, 188.2g manganese carbonate, after mixing with the 6000ml absolute ethyl alcohol, be placed on the corase grind machine and roughly grind 200min, slurry is moved in atomizer mill fine grinding 200min, take out material from the fine grinding machine, dry under 80 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 2:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 0.5Co 0.28Mn 0.16Si 0.03Zr 0.03O 1.98F 0.04363.2g lithium carbonate, the 10.6g lithium fluoride, the 382.1g nickel protoxide, the 230.0g cobaltosic oxide, the 32.9g zirconia, 18.4g silicon dioxide, the 188.2g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, roughly grind 200min on the corase grind machine, after raw material is mixed, take out material from the corase grind machine, dry under 80 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 3:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 0.5Co 0.28Mn 0.16Si 0.03Zr 0.03O 1.98F 0.04363.2g lithium carbonate, the 10.6g lithium fluoride, the 382.1g nickel protoxide, the 230.0g cobaltosic oxide, the 32.9g zirconia, 18.4g silicon dioxide, the 188.2g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out, add the 6000ml absolute ethyl alcohol, roughly grind 200min on the corase grind machine, will expect to move in atomizer mill, fine grinding 200min is dry under 80 ℃ with the compound after fine grinding.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 4:
Adopting lithium carbonate, manganese powder, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 0.78Co 0.08Mn 0.08Si 0.03Zr 0.03O 1.98F 0.04Weighing 355.9g lithium carbonate, the 10.6g lithium fluoride, 407.8 nickel protoxides, the 78.3g cobaltosic oxide, 32.9 zirconias, 18.4g silicon dioxide, the 73.0g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, roughly grind 150min on the corase grind machine, the material after corase grind is moved in atomizer mill, fine grinding 200min is dry under 100 ℃ with compound.The powder that obtains after dry is through 900 ℃ of roasting 20h, and is cooling with stove.
Specific embodiment 5:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares Li 1Ni 0.68Co 0.13Mn 0.11Al 0.05Zr 0.03O 1.98F 0.04Weighing 380.0g lithium carbonate, the 10.6g lithium fluoride, 466.2 metal nickel powders, the 48.0g metal cobalt powder, the 32.8g zirconia, 18.4g silicon dioxide, the 44.8g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, after corase grind 150min on the corase grind machine, will expect to move in atomizer mill, fine grinding 200min is dry under 100 ℃ with the compound after fine grinding.The powder that obtains after dry is through 900 ℃ of roasting 25h, and is cooling with stove.
Specific embodiment 6:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, metal nickel powder is that primary raw material prepares LiNi 0.58Co 0.18Mn 0.18Si 0.03Zr 0.03O 1.98F 0.04Weighing 363.2g lithium carbonate, the 10.6g lithium fluoride, 347.9 nickel, the 147.7g cobaltosic oxide, 32.9 zirconias, 18.4g silicon dioxide, the 211.5g manganese carbonate joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 12h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Carry out under 100 ℃ the compound after fine grinding dry.The powder that obtains after dry is through 950 ℃ of roasting 10h, and is cooling with stove.
Specific embodiment 7:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares LiNi 1/3Co 1/3Mn 1/3-0.06Al 0.04Mg 0.02O 1.985F 0.03Weighing 355.9g lithium carbonate, the 10.6g lithium fluoride, 407.8 nickel, the 78.3g cobalt, the 32.9g zirconia, 18.4g silicon dioxide, the 73.0g manganese carbonate joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 5000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 950 ℃ of roasting 5h, and is cooling with stove.
Specific embodiment 8:
Adopting lithium carbonate, manganese powder, metal cobalt powder, metal nickel powder is that primary raw material prepares LiNi 0.5Co 0.28Mn 0.15Al 0.04Zr 0.03O 1.98F 0.04Weighing 364.7g lithium carbonate, the 10.6g lithium fluoride, 301.1 metal nickel powders, the 169.3g metal cobalt powder, the 33.0g zirconia, the 20.9g alundum (Al2O3), the 84.5g manganese powder joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 950 ℃ of roasting 10h, and is cooling with stove.
Specific embodiment 9:
Adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 0.58Co 0.18Mn 0.18Al 0.03Mg 0.03O 1.98F 0.04375.2g lithium carbonate, the 10.9g lithium fluoride, the 453.5g nickel protoxide, the 151.2g cobaltosic oxide, 26.5g magnesium carbonate, the 16.0g alundum (Al2O3), the 216.6g manganese carbonate joins in pre-grinding jar, adds the 3500ml absolute ethyl alcohol, is placed on pre-grinding 5h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 100min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 900 ℃ of roasting 8h, and is cooling with stove.
Specific embodiment 10:
Adopting lithium carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares Li 1.04Ni 0.76Co 0.16Al 0.03Mg 0.03O 1.985F 0.03387.5g lithium carbonate, the 8.08g lithium fluoride, the 605.0g nickel protoxide, the 133.4g cobaltosic oxide, 26.3g magnesium carbonate, the 15.9g alundum (Al2O3) joins in pre-grinding jar, adds the 3000ml absolute ethyl alcohol, is placed on pre-grinding 24h on the bar type ball mill.Material after pre-grinding is taken out from pre-grinding jar, add the 6000ml absolute ethyl alcohol, fine grinding 200min on the fine grinding machine after raw material is mixed, takes out material from the fine grinding machine.Compound after fine grinding is dry under 100 ℃.The powder that obtains after dry is through 900 ℃ of roasting 12h, and is cooling with stove.
Specific embodiment 11:
Adopt the material of specific embodiment 1-10 preparation as active material, with the proportioning weighing according to 88: 7: 5 of conductive agent (SP), binding agent (PVDF), first active material and conductive agent are dry mixed 4h, PVDF is dissolved in the N-N dimethyl formamide, then the conductive agent with the active material that mixes adds wherein, stirs, and is coated on aluminium foil, dry in drying box, as the positive pole of battery.
Specific embodiment 12: the positive pole that embodiment 11 is prepared after drying, adopts the graphite conduct to electrode in vacuum drying oven, and the composition of electrolyte is mainly the LiPF of 1M 6And DMC/EC.Charging and discharging currents density 0.2C, discharging and recharging upper and lower limit voltage is 2.5-4.3V, specific capacity computational methods C=mA * h/g, wherein C: specific capacity, temperature is 25 ± 2 ℃, the constant current tester that computerizeds control carries out electrochemistry capacitance and loop test.
Comparative Examples 1: adopting lithium carbonate, manganese carbonate, cobaltosic oxide, nickel protoxide is that primary raw material prepares LiNi 1/3Co 1/3Mn 1/3O 2Weighing 19.2g lithium carbonate, 12.9g nickel protoxide, 13.9g cobaltosic oxide, 19.8g manganese carbonate is put into ball mill, adds the mixture of 100 milliliters of absolute ethyl alcohols and water, adds the 60g agate ball, wet-milling 2 hours is taken out, and puts into corundum crucible after 120 ℃ of oven dry, put into high temperature furnace and carry out sintering, be warmed up to 1000 ℃ by 4 ℃/minutes intensification speed, be incubated 10 hours, cooling is taken out, and grinds, cross 300 mesh sieves, obtain end product.
Comparative Examples 2: press chemical formula Li (Ni 1/3Co 1/3Mn 1/3) 0.99Mg 0.01O 1.99F 0.01Synthesized 16 hours under 900 ℃ in air after taking appropriate lithium carbonate, nickel hydroxide cobalt manganese, lithium fluoride, magnesium hydroxide mixing, cooling is taken out, and 300 mesh sieves are crossed in grinding, obtain end product.
Table 1 is the nickel-base anode material that synthesizes by composition of the present invention and method and the discharge capacity contrast that contrasts sample.The result of table 1 demonstrates with composition of the present invention and the synthetic nickel-base anode material of method has performance preferably.
Table 1
Discharge capacity mAhg first -1
Embodiment 1 165
Embodiment 2 170
Embodiment 3 178
Embodiment 4 198
Embodiment 5 183
Comparative Examples 1 148
Comparative Examples 2 160

Claims (13)

1. nickel-base anode material, it consists of: Li aNi bCo cMn dM eM’ fO 2-g/2F g, wherein M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05<e+f≤0.2,0.02<g≤0.1.
2. a kind of nickel-base anode material according to claim 1, is characterized in that: 0.05<e+f≤0.1,0.02<g≤0.05.
3. a kind of nickel-base anode material according to claim 1, it is characterized in that described M is: at least a in Ti, Zr, Al, Fe, Si, described M ' is: at least a in Mg, Ca, W.
4. a kind of nickel-base anode material according to claim 1, is characterized in that, described nickel-base anode material is a kind of in following composition: LiNi 0.5Co 0.28Mn 0.16Si 0.03Zr 0.03O 1.98F 0.04, LiNi 0.58Co 0.18Mn 0.18Si 0.03Zr 0.03O 1.98F 0.04, LiNi 0.68Co 0.13Mn 0.13Si 0.03Zr 0.03O 1.98F 0.04, LiNi 0.78Co 0.08Mn 0.08Si 0.03Zr 0.03O 1.98F 0.04, LiNi 0.68Co 0.13Mn 0.11Al 0.05Zr 0.03O 1.98F 0.04, LiNi 0.5Co 0.28Mn 0.15Al 0.04Zr 0.03O 1.98F 0.04, LiNi 0.86Co 0.08Al 0.03Mg 0.03O 1.975F 0.05, LiNi 0.58Co 0.18Mn 0.18Al 0.03Mg 0.03O 1.98F 0.04, Li 0.98Ni 0.78Co 0.16Si 0.02Al 0.02Mg 0.03O 1.975F 0.05, Li 1.04Ni 0.76Co 0.16Al 0.03Mg 0.03O 1.985F 0.03, LiNi 1/3Co 1/3Mn 1/3-0.06Al 0.04Mg 0.02O 1.985F 0.03
5. method for preparing the described nickel-base anode material of claim 1, it is characterized in that containing at least following 4 steps: 1) respectively with lithium source, manganese source, cobalt source, nickel source, with be selected from Ti source, Zr source, Al source, Fe source, Cr source, Si source, Cu source at least a, and be selected from least a in Mg source, Ca source, Sr source, Ba source, W source and the F source as raw material, according to the chemical expression Li of the described nickel-base anode material of claim 1 aNi bCo cMn dM eM’ fO 2-g/2F g, mole proportioning of requirement takes corresponding raw material; Wherein, M is at least a in Ti, Zr, Al, Fe, Cr, Si, Cu; M ' is at least a in Mg, Ca, Sr, Ba, W, and 0.95≤a≤1.2,0.2≤b≤0.9,0≤c≤0.4,0≤d≤0.4,0.05<e+f≤0.2,0.02<g≤0.1; 2) add solution to carry out wet-milling in raw material; 3) slurry with milled carries out drying; 4) dried material is synthesized under high temperature, the roasting synthesis temperature is 500-1100 ℃.
6. nickel-base anode material preparation method according to claim 5, is characterized in that described step 3) in the temperature of drying be 80-250 ℃.
7. nickel-base anode material preparation method according to claim 5, is characterized in that, described lithium source is anhydrous lithium hydroxide, contain crystallization water lithium hydroxide, at least a in lithium carbonate, described manganese source is manganese metal, manganese monoxide, manganese dioxide, at least a in manganese carbonate, described cobalt source is metallic cobalt, cobalt sesquioxide, cobaltosic oxide, cobalt protoxide, cobalt hydroxide, at least a in cobalt carbonate, described nickel source is metallic nickel, nickel sesquioxide, nickel protoxide, nickel hydroxide, at least a in nickelous carbonate, described titanium source is titanium dioxide, and described zirconium source is zirconia, and described aluminium source is metallic aluminium, alundum (Al2O3), at least a in aluminium hydroxide, described source of iron is iron oxide, ferrous oxide, iron hydroxide, at least a in ferrous hydroxide, described chromium source is crome metal, chrome green, at least a in chromium hydroxide, described silicon source is silicon dioxide, and described copper source is cupric oxide, cuprous oxide, at least a in copper carbonate, described magnesium source is magnesium carbonate, at least a in magnesium oxide, described calcium source is calcium carbonate, calcium oxide, at least a in calcium hydroxide, described strontium source is strontium carbonate, at least a in strontium oxide strontia, described barium source is brium carbonate, and described tungsten source is tungstic acid, and described fluorine source is lithium fluoride.
8. nickel-base anode material preparation method according to claim 5, is characterized in that described step 2) in wet-milling comprise at least in pre-grinding, corase grind, fine grinding two kinds; Wherein, pre-grinding is the average grain diameter D that makes particle in slurry 50Less than 3 μ m; Corase grind is the average grain diameter D that makes particle in slurry 50Less than 1 μ m; Fine grinding is the average grain diameter D that makes particle in slurry 50Less than 0.1 μ m.
9. nickel-base anode material preparation method according to claim 5, is characterized in that, described drying is at least a in forced air drying, vacuumize, spray drying.
10. nickel-base anode material preparation method according to claim 5, is characterized in that, the synthetic temperature of roasting is 800-1000 ℃.
11. nickel-base anode material preparation method according to claim 5 is characterized in that, the synthetic temperature of roasting is 800-900 ℃.
12. a positive pole is characterized in that, the described nickel-base anode material of claim 1 is mixed with conductive agent and bonding agent, and the mixture that obtains is coated in the positive pole that supports formation lithium ion battery on conducting base.
13. a battery is characterized in that, anode, barrier film, electrolyte that the described positive pole of claim 12 is compatible with electricity are placed in container and form lithium ion battery.
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