CN103456945A - Preparation method of low-cost lithium ion battery anode material - Google Patents
Preparation method of low-cost lithium ion battery anode material Download PDFInfo
- Publication number
- CN103456945A CN103456945A CN2013104133347A CN201310413334A CN103456945A CN 103456945 A CN103456945 A CN 103456945A CN 2013104133347 A CN2013104133347 A CN 2013104133347A CN 201310413334 A CN201310413334 A CN 201310413334A CN 103456945 A CN103456945 A CN 103456945A
- Authority
- CN
- China
- Prior art keywords
- lithium
- sintering
- preparation
- low
- manganese
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a preparation method of a low-cost lithium ion battery anode material. The chemical composition of the material is LizNa1-zMn2-kAlkO4, wherein z is greater than or equal to 0.8 and smaller than 1.0, and k is greater than 0.0 and smaller than or equal to 0.6. The preparation method comprises the following steps: (1) blending a lithium source, a sodium source, a manganese source and an aluminum source according to a mole ratio of (1+w)z: (1+v)(1-z): (2-k): k, and ball-milling in a ball mill to obtain a mixed material, wherein w is greater than 0 and smaller than or equal to 0.1, and v is greater than 0 and smaller than or equal to 0.1; (2) sintering the mixed material of the step (1) at the temperature of 250-350 DEG C for 1-5 hours for the first time, and then sintering at the temperature of 750-900 DEG C for 6-24 hours for the second time, wherein the sintering atmosphere is air; (3) naturally cooling the material after the second sintering of the step (2). The finished product prepared by the method consists of five low-cost and environment-friendly elements, and is environment-friendly, low in cost, and long in cycle life, and the preparation technology is simple.
Description
Technical field
The present invention relates to a kind of preparation method of low-cost anode material for lithium-ion batteries, belong to the technical field of ion battery material.
Background technology
The positive electrode of commercial Li-ion battery comprises cobalt acid lithium, LiMn2O4, ternary layered positive pole etc.The price of cobalt acid lithium is very high, mainly is used in the lithium ion battery of high-end electronic devices at present.Preparation technology's relative complex of ternary layered positive electrode, used mainly as auxiliary positive electrode.The cycle performance of pure spinel lithium manganate is poor, generally by replace the wherein way of part manganese element with other metallic element, improves its cyclical stability, so derive the doping type spinel lithium manganate, its composition is expressed as LiMn
2-xm
xo
4, common M element is cobalt, aluminium, magnesium, nickel etc.
But, the way that partly replaces manganese by other metallic element is improved cycle performance, there is following shortcoming: 1) from synthetic angle, the element formed is more, requirement to synthesis condition is higher, and synthetic more difficult, the consistency between the different batches product more is difficult to ensure card, in product, the uniformity of component distributing also more is difficult to ensure card, and the while is more difficult control phase segregation phenomenon also; 2) spinel lithium manganate is that its cost is low in the advantage of the maximum in industrialization field, introduces other metallic element and may increase raw-material cost, makes it lose competitive advantage; 3) constituent of pure spinel lithium manganate is all nontoxic, has obvious advantage aspect environmental protection, introduces other metallic element and easily causes environmental pollution.
Chinese patent literature CN1773749A(200410065723.6) preparation method of the spinel type lithium manganate cell positive electrode material of a kind of Sc (III) doping is disclosed, with LiOHH
2o, MnO
2for initial material, press LiScxMn
2-xo
4the amount ratio, x=0.01-0.2, mix Sc2O3,450-500 ℃ of calcination 3-6 hour after grinding, then 500-550 ℃ of calcination 3-6 hour after grinding, 600-800 ℃ of calcination 12-24 hour after grinding; Or mix Sc
2o
3the time by every mole of initial material, add the 100-200 milliliter by ethanol: the distilled water volume ratio is the mixed dispersant formed at 2: 3,600-800 ℃ of calcination 12-24 hour after grinding; Obtain end product.This method preparation process is simple, and reaction time is short, has significantly improved the cycle performance of spinel-type lithium-ion cell positive material, the spinel structure still remained intact after 60 circulations, and prospects for commercial application is good.But scandium (Sc) belongs to somewhat expensive rare earth element, introduce Sc (III) cost higher.
Chinese patent literature CN102593460A(201210050634.9) a kind of preparation method of doping vario-property lithium manganate having spinel structure is disclosed, comprise, Li source compound, manganese source compound, doped metal salt and roasting promoter are mixed to get to mixture, then described mixture roasting are obtained to the lithium manganate having spinel structure of doped metallic elements; Wherein said roasting promoter comprises: one or more in acetylene black, activated carbon powder, coke blacking and charcoal powder.Preparation method provided by the invention, sintering temperature is low, and roasting time is short, the constant product quality of the doping vario-property lithium manganate having spinel structure simultaneously obtained, performance homogeneous.
Chinese patent literature CN102730764A(201210216049.1) a kind of nano level modified lithium manganate having spinel structure material and preparation method thereof is disclosed, be specifically related to Mg, Zn, several in the metals such as Al carry out composite doping modification according to certain combination to spinelle, belong to technical field of lithium batteries.It mixes the acetate of ,Meng source, lithium source and metal M or nitrate after levigate in the mol ratio mortar, add deionized water and citric acid, after regulating pH with concentrated ammonia liquor, heating evaporation obtains wet gel, obtain xerogel after the wet gel drying, after twice calcination ground, obtain the product modified spinelle manganic acid lithium material.Preparation method provided by the invention belongs to the nanoscale scope, thereby has higher specific discharge capacity and good high rate performance; Composite mixed, can improve its cycle performance and high-temperature behavior, thereby there is great practical application meaning.
Chinese patent literature CN102903902A(201210366006.1) disclose a kind of doping type spinel lithium manganate electrode material and preparation method thereof, wherein the molecular formula of doping type spinel lithium manganate electrode material is LiMn
2-x-ym
xn
yo
4, in formula, M and N are doped chemical and are selected from any two kinds in Al, Mg, Cr, Co, 0<x+y in formula<0.6.Doping type spinel lithium manganate electrode material of the present invention, two metallic element M, N can significantly improve the structure of pure LiMn2O4 as table phase alloy, further reduce by the ratio of 3 valency Mn, increase the stability of structure, suppress the Jahn-Teller effect; Suppress the Mn dissolving of LiMn2O4 surface simultaneously, thereby improved cycle performance and the high temperature performance of LiMn2O4, table adulterates mutually and can, in the situation that equal doping effect reduces doping, be conducive to reduce material cost simultaneously.The application of spinel type lithium manganate electrode material of the present invention, is characterized in that being applicable to electric tool and the electric vehicle lithium battery that power is larger.
But the disclosed electrode material of above-mentioned patent documentation mainly contains following deficiency: 1, the synthetic homogeneity of sample is difficult to guarantee, synthetic cost is higher; The element atomic weight of introducing is much larger than the atomic weight of Mn, or the element of introducing is inert element, can cause the obvious reduction of material available capacity; 2, introduce the poisonous element such as Cr, can cause the pollution of environment, increased the toxicity of material.
Chinese patent literature CN101780983A(200910105112.2) a kind of spinelle Li is disclosed
1+xm
ymn
2-x-yo
4, wherein, 0<x<0.1,0<y<0.1, M is selected from one or more in Mg, Na, Co, Al, it is characterized in that, described Li
1+xm
ymn
2-x-yo
4400 crystal face diffraction peak intensity I400 and the ratio of 311 crystal face diffraction peak intensity I311 be 1.05～1.25.But this material is the non-stoichiometric material, low Mn stoichiometric proportion can obviously reduce the available capacity of material and be difficult to synthesize, and especially is difficult to realize the synthetic of bulk article.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of preparation method of low-cost anode material for lithium-ion batteries, especially provide a kind of low cost, pollution-free, long circulation life, doped with the spinel lithium manganate cell positive material Li of aluminium and sodium
zna
1-zmn
2-kal
ko
4the preparation method.
Terminological interpretation:
Nitrogen is cold soon: be that material to be cooled is put into to liquid nitrogen is cooling.
Technical scheme of the present invention is as follows:
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
zna
1-zmn
2-kal
ko
4, wherein, 0.8≤z<1.0,0.0<k≤0.6; Preparation process is as follows:
(1) press the lithium source: the sodium source: the manganese source: the z:(1+v of aluminium source=(1+w)) (1-z): (2-k): the molar ratio batching of k, in ball mill, ball milling obtains mixed material; 0<w≤0.1,0<v≤0.1;
(2) by the mixed material of step (1) in 250～350 ℃ of first sinterings 1～5 hour, and then, at 750～900 ℃ of sintering 6～24 hours for the second time, sintering atmosphere is air;
(3) by step (2), the material after sintering is naturally cooling and get final product for the second time;
Perhaps, by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling, and then continue sintering 4～8 hours at 750～900 ℃, naturally cooling or adopt nitrogen soon cold mode be cooled to room temperature and get final product;
Perhaps, the material after step (2) sintering is adopted the fast cold mode of nitrogen be cooled to room temperature and get final product.
According to the present invention, the chemical composition Li of described anode material for lithium-ion batteries
zna
1-zmn
2-kal
ko
4, preferred, z=0.94, k=0.3.
In step of the present invention (1), preferred, described lithium source is selected from one or more in lithium carbonate, lithium oxalate, lithium acetate;
Preferably, described sodium source is selected from one or more in sodium carbonate, sodium oxalate, sodium acetate;
Preferably, described manganese source is selected from one or more in manganese carbonate, manganous hydroxide, hydrogen oxide manganese oxide, manganese dioxide, manganese sesquioxide managnic oxide, manganese oxalate, manganese acetate;
Preferably, described aluminium source is selected from one or more in aluminium oxide, aluminium hydroxide, aluminum nitrate.
According to the present invention, preferred, the lithium source described in step (1): sodium source: manganese source: the mol ratio in aluminium source is 0.94:0.066:1.7:0.3.
According to the present invention, preferred, in step (2), the first sintering temperature is 250 ℃, and sintering time is 5h; Sintering temperature is 800 ℃ for the second time, and sintering time is 24h.
The loss that Yu Na source, lithium source is excessive in step of the present invention (1) while taking to make up pyroreaction, w, v are excessive number; Adopt double sintering in step (2), first sintering at a lower temperature is to prevent containing because of raw material the bumping that a certain amount of moisture causes; Adopt in step (3) the fast cold or double sintering of nitrogen can obviously improve the cyclical stability of product.
Beneficial effect of the present invention:
1, the present invention's adulterated al optionally, the atomic weight of aluminium is less, can obviously not reduce the available capacity of material, and aluminium can improve the average valence of manganese, reduces the Jahn-Teller effect, can obviously improve the cycle performance of product.
2, the present invention's sodium contaminated optionally, the less available capacity that also can obviously not reduce material of the atomic weight of sodium; The radius of sodium ion is greater than lithium ion, and in charge and discharge cycles, sodium ion can not participate in electrochemical reaction, and the sodium ion in lattice can increase the distance between manganese ion, weakens the Jahn-Teller effect, thereby improves cycle life.
3, the finished product that prepared by the present invention is low by 5 kinds of prices, the environment-friendly type element forms, i.e. lithium, sodium, manganese, aluminium, oxygen have environmental protection, price is low, preparation technology is simple, product circulation life-span advantages of higher.
Embodiment
Below by specific embodiment, the present invention will be further described, but be not limited to this.
Raw materials usedly in embodiment be conventional commercial reagent.
Embodiment 1
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.9na
0.1mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium carbonate: sodium carbonate: manganese carbonate: the mol ratio of aluminium hydroxide is that 0.909:0.101:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 350 ℃ of air, and then at 900 ℃ of sintering 24 hours for the second time;
(3) by step (2), the material after sintering is naturally cooling and get final product for the second time.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 138mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 80%.
Embodiment 2
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.9na
0.1mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium carbonate: sodium carbonate: manganese carbonate: the mol ratio of aluminium hydroxide is that 0.909:0.101:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 350 ℃ of air, and then at 900 ℃ of sintering 24 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 30 minutes, and then 900 ℃ of sintering 6 hours, naturally cooling and get final product.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 135.3mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 83.5%.
Embodiment 3
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.9na
0.1mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium carbonate: sodium carbonate: manganese carbonate: the mol ratio of aluminium hydroxide is that 0.909:0.101:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 350 ℃ of air, and then at 900 ℃ of sintering 24 hours for the second time;
(3) by step (2) for the second time the material after sintering adopt the fast cold mode of nitrogen be cooled to room temperature and get final product, the fast cold mode of nitrogen is cooling for directly sample being immersed in liquid nitrogen.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 118mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 88%.
Embodiment 4
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.9na
0.1mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium carbonate: sodium carbonate: manganese carbonate: the mol ratio of aluminium hydroxide is that 0.99:0.11:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 350 ℃ of air, and then at 900 ℃ of sintering 24 hours for the second time;
(3) by step (2), the material after sintering is naturally cooling and get final product for the second time.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 135mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 82%.
Embodiment 5
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.8na
0.2mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium oxalate: sodium oxalate: manganese oxalate: the mol ratio of aluminum nitrate is that 0.84:0.21:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 1 hour in 300 ℃ of air, and then at 750 ℃ of sintering 6 hours for the second time;
(3) by step (2), the material after sintering is naturally cooling and get final product for the second time.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 128mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 85.9%.
Embodiment 6
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.9na
0.1mn
1.9al
0.1o
4, preparation process is as follows:
(1) by lithium acetate: sodium carbonate: manganese dioxide: the mol ratio of aluminium hydroxide is that 0.909:0.101:1.9:0.1 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 250 ℃ of air, and then at 800 ℃ of sintering 6 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 30 minutes, and then 800 ℃ of sintering 6 hours, naturally cooling and get final product.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 127.9mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 83.2%.
Embodiment 7
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.94na
0.06mn
1.7al
0.3o
4, preparation process is as follows:
(1) by lithium acetate: sodium carbonate: manganese dioxide: the mol ratio of aluminium hydroxide is that 0.987:0.063:1.7:0.3 takes chemical reagent, and then in ball mill, ball milling obtains mixed material in 30 minutes;
(2) by the mixed material of step (1) first sintering 5 hours in 250 ℃ of air, and then at 800 ℃ of sintering 6 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 30 minutes, and then 800 ℃ of sintering 6 hours, naturally cooling and get final product.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 110.9mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 87.7%.
Embodiment 8
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.94na
0.06mn
1.7al
0.3o
4, preparation process is as follows:
(1) by lithium acetate: sodium carbonate: manganous hydroxide: the mol ratio of aluminium hydroxide is that 0.987:0.063:1.7:0.3 takes chemical reagent, and then in ball mill, ball milling 1h obtains mixed material;
(2) by the mixed material of step (1) first sintering 5 hours in 250 ℃ of air, and then at 800 ℃ of sintering 6 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 1h, and then 800 ℃ of sintering 6 hours, naturally cooling and get final product.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 109.1mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 90.5%.
Embodiment 9
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.94na
0.06mn
1.7al
0.3o
4, preparation process is as follows:
(1) by lithium acetate: sodium carbonate: manganous hydroxide: the mol ratio of aluminium hydroxide is that 0.987:0.063:1.7:0.3 takes chemical reagent, and then in ball mill, ball milling 2h obtains mixed material;
(2) by the mixed material of step (1) first sintering 5 hours in 250 ℃ of air, and then at 800 ℃ of sintering 24 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 2h, and then 800 ℃ of sintering 6 hours, naturally cooling and get final product.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 112.6mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 90.3%.
Embodiment 10
A kind of preparation method of low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
0.94na
0.06mn
1.7al
0.3o
4, preparation process is as follows:
(1) by lithium acetate: sodium carbonate: manganous hydroxide: the mol ratio of aluminium hydroxide is that 0.987:0.063:1.7:0.3 takes chemical reagent, and then in ball mill, ball milling 3h obtains mixed material;
(2) by the mixed material of step (1) first sintering 5 hours in 250 ℃ of air, and then at 800 ℃ of sintering 24 hours for the second time;
(3) by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling 3h, then, 800 ℃ of sintering 24 hours, adopt the fast cold mode of nitrogen be cooled to room temperature and get final product; The fast cold mode of nitrogen is for to immerse in liquid nitrogen cooling by sample.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 108.3mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 92.1%.
Comparative Examples 1
The preparation of this Comparative Examples is doped with the spinel lithium manganate electrode material of magnesium and sodium, and raw material is lithium acetate: sodium carbonate: manganese oxalate: magnesium hydroxide=0.987:0.063:1.7:0.3 mol ratio, preparation process is with embodiment 9.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 117mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 78%.
Comparative Examples 2
The preparation of this Comparative Examples is doped with the spinel lithium manganate electrode material of magnesium and sodium, raw material is lithium acetate: sodium carbonate: manganese oxalate: magnesium nitrate=0.987:0.063:1.7:0.3 mol ratio, preparation process is with embodiment 9, different is that in step (2), the temperature of first sintering is 650 ℃, and sintering temperature is 900 ℃ for the second time.
Take the product that obtains as anodal (positive pole consists of active material: the PVDF binding agent: the mass ratio of SuperP conductive agent is 8:1:1), take 1M liPF6/EC+DEC as electrolyte, the Celgard2400 barrier film, lithium metal is to electrode, be assembled into 2032 button cells, 0.1C under multiplying power, to record initial capacity be 118.6mAh/g to the 3.6-4.3V scope, the capability retention after 100 times that circulates is 81.2%.
Claims (9)
1. the preparation method of a low-cost anode material for lithium-ion batteries, the chemical composition of described anode material for lithium-ion batteries is Li
zna
1-zmn
2-kal
ko
4, wherein, 0.8≤z<1.0,0.0<k≤0.6; Preparation process is as follows:
(1) press the lithium source: the sodium source: the manganese source: the z:(1+v of aluminium source=(1+w)) (1-z): (2-k): the molar ratio batching of k, in ball mill, ball milling obtains mixed material; 0<w≤0.1,0<v≤0.1;
(2) by the mixed material of step (1) in 250～350 ℃ of first sinterings 1～5 hour, and then, at 750～900 ℃ of sintering 6～24 hours for the second time, sintering atmosphere is air;
(3) by step (2), the material after sintering is naturally cooling and get final product for the second time;
Perhaps, by step (2) for the second time the material after sintering naturally cooling after in ball mill ball milling, and then continue sintering 4～8 hours at 750～900 ℃, naturally cooling or adopt nitrogen soon cold mode be cooled to room temperature and get final product;
Perhaps, the material after step (2) sintering is adopted the fast cold mode of nitrogen be cooled to room temperature and get final product.
2. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the chemical composition Li of described anode material for lithium-ion batteries
zna
1-zmn
2-kal
ko
4, z=0.94, k=0.3.
3. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the lithium source described in step (1) is selected from one or more in lithium carbonate, lithium oxalate, lithium acetate.
4. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the sodium source described in step (1) is selected from one or more in sodium carbonate, sodium oxalate, sodium acetate.
5. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, it is characterized in that, the manganese source described in step (1) is selected from one or more in manganese carbonate, manganous hydroxide, hydrogen oxide manganese oxide, manganese dioxide, manganese sesquioxide managnic oxide, manganese oxalate, manganese acetate.
6. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the aluminium source described in step (1) is selected from one or more in aluminium oxide, aluminium hydroxide, aluminum nitrate.
7. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the He Lv source, manganese source described in step (1) also comprises the mixed hydroxides of manganese, aluminium.
8. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, the lithium source described in step (1): sodium source: manganese source: the mol ratio in aluminium source is 0.94:0.066:1.7:0.3.
9. the preparation method of low-cost anode material for lithium-ion batteries according to claim 1, is characterized in that, in step (2), the first sintering temperature is 250 ℃, and sintering time is 5h; Sintering temperature is 800 ℃ for the second time, and sintering time is 24h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104133347A CN103456945A (en) | 2013-09-11 | 2013-09-11 | Preparation method of low-cost lithium ion battery anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2013104133347A CN103456945A (en) | 2013-09-11 | 2013-09-11 | Preparation method of low-cost lithium ion battery anode material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103456945A true CN103456945A (en) | 2013-12-18 |
Family
ID=49739088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2013104133347A Pending CN103456945A (en) | 2013-09-11 | 2013-09-11 | Preparation method of low-cost lithium ion battery anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103456945A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103928675A (en) * | 2014-04-18 | 2014-07-16 | 东莞市迈科科技有限公司 | Lithium nickel manganese oxide anode material and preparation method thereof |
| CN103943845A (en) * | 2014-04-18 | 2014-07-23 | 江苏大学 | Preparation method of layered-spinel composite solid solution positive-electrode material |
| CN104617262A (en) * | 2014-12-17 | 2015-05-13 | 宁波维科电池股份有限公司 | Multivariate material composite positive electrode and lithium ion battery |
| CN105428641A (en) * | 2015-12-10 | 2016-03-23 | 桂林理工大学 | Method for preparing lithium manganese oxide cathode material by synergistically doping aluminum and sodium with high rate performance |
| CN105745174A (en) * | 2013-11-22 | 2016-07-06 | 三井金属矿业株式会社 | Spinel-type lithium metal composite oxide |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000133266A (en) * | 1998-10-28 | 2000-05-12 | Mitsubishi Materials Corp | Positive active material of lithium secondary battery and manufacture of same |
| US20020012843A1 (en) * | 2000-03-03 | 2002-01-31 | Nissan Motor Co., Ltd. And | Positive electrode material and battery for nonaquous electrolyte secondary battery |
| CN102473905A (en) * | 2009-07-14 | 2012-05-23 | 川崎重工业株式会社 | Electrical storage device provided with fiber electrodes, and method for producing same |
| CN102659183A (en) * | 2012-03-06 | 2012-09-12 | 苏州大学 | Method for preparing cathode material Li1-x-yNaxKyMn2O4 |
| CN102723494A (en) * | 2012-07-05 | 2012-10-10 | 河北善鑫泰瑞电池科技有限公司 | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof |
| CN102945953A (en) * | 2012-08-29 | 2013-02-27 | 广州市香港科大霍英东研究院 | Novel preparation method of high temperature-type long-life lithium ion battery anode material LiMn2-x-yMIxMIIyO4 |
-
2013
- 2013-09-11 CN CN2013104133347A patent/CN103456945A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000133266A (en) * | 1998-10-28 | 2000-05-12 | Mitsubishi Materials Corp | Positive active material of lithium secondary battery and manufacture of same |
| US20020012843A1 (en) * | 2000-03-03 | 2002-01-31 | Nissan Motor Co., Ltd. And | Positive electrode material and battery for nonaquous electrolyte secondary battery |
| CN102473905A (en) * | 2009-07-14 | 2012-05-23 | 川崎重工业株式会社 | Electrical storage device provided with fiber electrodes, and method for producing same |
| CN102659183A (en) * | 2012-03-06 | 2012-09-12 | 苏州大学 | Method for preparing cathode material Li1-x-yNaxKyMn2O4 |
| CN102723494A (en) * | 2012-07-05 | 2012-10-10 | 河北善鑫泰瑞电池科技有限公司 | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof |
| CN102945953A (en) * | 2012-08-29 | 2013-02-27 | 广州市香港科大霍英东研究院 | Novel preparation method of high temperature-type long-life lithium ion battery anode material LiMn2-x-yMIxMIIyO4 |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105745174A (en) * | 2013-11-22 | 2016-07-06 | 三井金属矿业株式会社 | Spinel-type lithium metal composite oxide |
| CN103928675A (en) * | 2014-04-18 | 2014-07-16 | 东莞市迈科科技有限公司 | Lithium nickel manganese oxide anode material and preparation method thereof |
| CN103943845A (en) * | 2014-04-18 | 2014-07-23 | 江苏大学 | Preparation method of layered-spinel composite solid solution positive-electrode material |
| CN104617262A (en) * | 2014-12-17 | 2015-05-13 | 宁波维科电池股份有限公司 | Multivariate material composite positive electrode and lithium ion battery |
| CN105428641A (en) * | 2015-12-10 | 2016-03-23 | 桂林理工大学 | Method for preparing lithium manganese oxide cathode material by synergistically doping aluminum and sodium with high rate performance |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109980219B (en) | Full-gradient nickel-cobalt-manganese positive electrode material, ruthenium oxide coating material and preparation method thereof | |
| CN101335348B (en) | Preparing method of lithium ionic cell 5V anode material spherical LiNi0.5Mn1.5O4 | |
| CN102044671B (en) | Spinel type lithium manganate electrode material and preparation method thereof | |
| CN102088085B (en) | Lithium ion battery positive material and preparation method thereof | |
| CN109473657A (en) | A kind of nickel cobalt aluminium manganese quaternary lithium-ion battery positive electrode material being mixed with, Preparation method and use | |
| CN102332585A (en) | Lithium nickel cobalt manganese oxygen/stannic oxide composite anode material doped with metal elements and method for preparing lithium nickel cobalt manganese oxygen/stannic oxide composite anode material | |
| CN103117380A (en) | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery | |
| CN102437323A (en) | Anode material of lithium ion battery and preparation method thereof | |
| CN105185954A (en) | LiAlO2 coated LiNi1-xCoxO2 lithium-ion battery positive electrode material and preparation method thereof | |
| CN102034967A (en) | Coprecipitation preparation method of nickel manganese lithium oxide of anode material of high-voltage lithium battery | |
| CN102637867A (en) | Chromium-doped lithium-nickel-manganese-oxygen material and preparation method thereof, and lithium ion battery containing chromium-doped lithium-nickel-manganese-oxygen material | |
| CN102208611A (en) | Induced crystallization synthesis method for anode powder material of lithium ion secondary battery | |
| CN104425809A (en) | Lithium ion battery positive electrode material, preparation method of lithium ion battery positive electrode material, lithium ion battery comprising lithium ion battery positive electrode material | |
| CN103606663A (en) | Multiplying-power lithium-rich composite anode material and preparation method thereof | |
| CN103022471B (en) | Improve the method for nickelic tertiary cathode material chemical property | |
| CN103078099A (en) | Anode material for lithium ion cell and preparation method thereof | |
| CN102723494A (en) | Doped and modified high-temperature lithium manganate cathode material and preparation method thereof | |
| CN102709525A (en) | Metal oxide coated lithium nickel manganese oxide material, preparation method of metal oxide coated lithium nickel manganese oxide material and lithium ion battery | |
| CN103219507A (en) | Composite material with tubular structure as well as preparation method and application thereof | |
| CN109065871A (en) | It is a kind of to be mixed with modified nickel cobalt lithium aluminate cathode material and preparation method thereof | |
| CN100537418C (en) | Preparation method of transition element doped iron lithium phosphate powder | |
| CN115207340A (en) | Sodium ion battery layered oxide positive electrode material and preparation method and application thereof | |
| CN103456945A (en) | Preparation method of low-cost lithium ion battery anode material | |
| CN103367733A (en) | Lithium ion battery cathode material and preparation method thereof and lithium ion battery | |
| CN110380037B (en) | Reaction infiltration modified lithium ion battery positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20131218 |