CN101540399A - Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof - Google Patents
Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof Download PDFInfo
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- CN101540399A CN101540399A CN200910020749A CN200910020749A CN101540399A CN 101540399 A CN101540399 A CN 101540399A CN 200910020749 A CN200910020749 A CN 200910020749A CN 200910020749 A CN200910020749 A CN 200910020749A CN 101540399 A CN101540399 A CN 101540399A
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Abstract
The invention relates to a manganic niobium doping type lithium manganate cathode material for a lithium-ion secondary battery and a preparation method thereof. The invention adopts a solid-phase method which is easy for industrialization and prepares cathode material lithium manganate powder for the manganic niobium doping type lithium-ion secondary battery with good crystallization performance and uniform ingredients through a simple ball milling and sintering process by controlling the ball milling time and the sintering temperature and time. The chemical general formula of the lithium battery cathode material is LiMn<2-x>NbxO4, wherein, x is larger than 0 but smaller than 0.2. Compared with common lithium manganate, the lithium battery cathode material has the characteristics of higher capacity, better circulation and more superior magnification performance and is easier for industrialized production.
Description
Technical field:
The present invention relates to manganic niobium doping type manganate cathode material for lithium of a kind of lithium rechargeable battery and preparation method thereof.
Background technology:
Traditional secondary cell mainly contains lead-acid battery, ickel-cadmium cell, Ni-MH battery etc., lower because of energy density, pollute the demand that problem such as bad border can not meet market well, lithium ion battery is owing to good combination property, meet the social development needs, and its range of application will be more and more widely.
And positive electrode is the important component part of lithium ion battery, accounts for 40% of lithium ion battery cost, also is the key of decision lithium ion battery performance.The positive electrode of practical application at present mainly is cobalt acid lithium (LiCoO
2), ternary material (LiNi
1/3Co
1/3Mn
1/3O
2), LiFePO4 (LiFePO
4) and LiMn2O4 (LiMn
2O
4).Cobalt acid lithium costs an arm and a leg because of cobalt resource lacks, and poor heat stability, has safety problem; The ternary material price is also higher, and poor heat stability, voltage platform are low; LiFePO4 poorly conductive and density are too low; Though tradition LiMn2O4 cost is low, fail safe good, capacity is lower, high temperature cyclic performance is poor.Therefore, need exploitation or improvement new type lithium ion battery positive electrode.
Summary of the invention:
The purpose of this invention is to provide manganic niobium doping type manganate cathode material for lithium of a kind of lithium rechargeable battery and preparation method thereof, the present invention utilizes solid phase method, and synthetic that traditional LiMn2O4 is carried out the manganese position is niobium-doped to its modification, product has improved capacity, high rate performance and the high temperature cyclic performance of LiMn2O4, method technology is simple, is easy to suitability for industrialized production.
The objective of the invention is to realize as follows: the manganic niobium doping type manganate cathode material for lithium of this lithium rechargeable battery, its nominal composition formula is LiMn
2-xNb
xO
4, wherein, doping scope 0＜x＜0.2.
The doping of manganese position is a kind of nominal composition amount in the synthetic doped compound.
The preparation method of the manganic niobium doping type manganate cathode material for lithium of above-mentioned lithium rechargeable battery is: get lithium compound, manganese compound and niobium compound, mol ratio according to element Li, Mn, Nb is: Li: [(2-x) Mn+xNb]=1: 2 raw materials weighing, wherein 0＜x＜0.2; The raw material that weighs up is added ball mill container, add ball-milling medium and dispersant then, mixing and ball milling 3～10 hours is 50～100 ℃ of oven dry down; Oven dry back powder is at 550～900 ℃ of following preroast 5-20 hours, and the semi-finished product that obtain are used dry method in ball mill ball milling 2-5 hour again, and then at 500～700 ℃ of following after baking 5-20 hours, the back of coming out of the stove is crossed 300 mesh sieves and promptly got target product.
Described dispersant is a kind of in deionized water, industrial alcohol and the absolute ethyl alcohol, or two or three mixture wherein.
Ball mill container is a kind of in corundum ball grinder, agate jar, polyurethane ball grinder, the nylon ball grinder.
Ball-milling medium is a kind of in zirconia ball, corundum ball, agate ball and the stainless steel ball.
Lithium compound is one or both and the two or more mixture in lithium carbonate, lithium oxalate, lithium acetate, the lithium hydroxide.
Described manganese compound is a kind of in electrolytic manganese dioxide, chemical manganese bioxide, the manganese sesquioxide managnic oxide, or two or three mixture.
Described niobium compound is a kind of in niobium hydroxide, niobium pentaoxide, the niobium oxalate.
The present invention adopts the solid phase method that is easy to industrialization, through simple ball milling, sintering process, by control ball milling time and sintering temperature and the time, prepare that crystal property is good, the uniform manganic niobium doping type secondary lithium battery positive-material lithium manganate powder of composition.Compare with traditional LiMn2O4, the present invention has significantly improved its capacity, cycle performance, high rate performance and high-temperature behavior.Be applicable to suitability for industrialized production simultaneously, have wide application prospect in secondary lithium battery field commonly used.
Embodiment:
Embodiment 1
By Li: Mn: Nb=1: 1.98: 0.05 mol ratio takes by weighing battery-level lithium carbonate (Li
2CO
3) 37.04g, electrolytic manganese dioxide (MnO
2) 177.4g, analysis pure zirconia niobium (Nb
2O
5) 6.6g mixes the back and add in the diamond spar ball grinder, add the 100ml absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 10 hours with the zirconia ball on the roller milling machine, discharging, muffle furnace is put in 80 ℃ of oven dry, 800 ℃ of following preroasts 15 hours, the semi-finished product that obtain are used dry method ball milling 3 hours in the polyurethane ball grinder again, and 680 ℃ of following after bakings 10 hours, the back of coming out of the stove was crossed 300 mesh sieves and promptly got target product then.Record its first reversible specific capacity be 120.8mAh/g, discharge and recharge 300 capacity and keep more than 90%, 300 capacity of high rate performance: 20C discharge keep 85%.
Embodiment 2
By Li: Mn: Nb=1: 1.98: 0.05 mol ratio takes by weighing battery-level lithium carbonate (Li
2CO
3) 37.04g, electrolytic manganese dioxide (MnO
2) 177.4g, analyze pure niobium oxalate (C
10H
5NbO
20) 26.9g mixes the back and add in the diamond spar ball grinder, add the 100ml absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 10 hours with the zirconia ball on the roller milling machine, discharging, 80 ℃ of oven dry, 800 ℃ of following preroasts 15 hours, the semi-finished product that obtain were used dry method ball milling 3 hours in the polyurethane ball grinder again, 680 ℃ of following after bakings 10 hours, the back of coming out of the stove was crossed 300 mesh sieves and was promptly got target product then.Record its first reversible specific capacity be 123.2mAh/g, discharge and recharge 300 capacity and keep more than 90%, 300 capacity of high rate performance: 20C discharge keep 85%.
Embodiment 3
By Li: Mn: Nb=1: 1.98: 0.05 mol ratio takes by weighing battery-level lithium carbonate (Li
2CO
3) 37.04g, chemical manganese bioxide (MnO
2) 177.4g, analysis pure zirconia niobium (Nb
2O
5) 6.6g mixes the back and add in the diamond spar mill jar, add the 100ml absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 10 hours with the zirconia ball on the roller milling machine, discharging, 80 ℃ of oven dry, 800 ℃ of following preroasts 15 hours, the semi-finished product that obtain were used dry method ball milling 3 hours in the polyurethane ball grinder again, 680 ℃ of following after bakings 10 hours, the back of coming out of the stove was crossed 300 mesh sieves and was promptly got target product then.Record its first reversible specific capacity be 125.8mAh/g, discharge and recharge 300 capacity and keep more than 92%, 300 capacity of high rate performance: 20C discharge keep 86%.
Embodiment 4
By Li: Mn: Nb=1: 1.98: 0.05 mol ratio takes by weighing battery-level lithium carbonate (Li
2CO
3) 37.04g, chemical manganese bioxide (MnO
2) 177.4g, analysis pure zirconia niobium (Nb
2O
5) 6.6g mixes the back and add in the diamond spar mill jar, add the 100ml absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 10 hours with the zirconia ball on the roller milling machine, discharging, 80 ℃ of oven dry, 800 ℃ of following preroasts 20 hours, the semi-finished product that obtain were used dry method ball milling 3 hours in the polyurethane ball grinder again, 680 ℃ of following after bakings 15 hours, the back of coming out of the stove was crossed 300 mesh sieves and was promptly got target product then.Record its first reversible specific capacity be 126.5mAh/g, discharge and recharge 300 capacity and keep more than 94%, 300 capacity of high rate performance: 20C discharge keep 86.5%.
Embodiment 5
By Li: Mn: Nb=1: 1.98: 0.1 mol ratio takes by weighing battery-level lithium carbonate (Li
2CO
3) 37.04g, chemical manganese bioxide (MnO
2) 177.4g, analysis pure zirconia niobium (Nb
2O
5) 13.2g mixes the back and add in the diamond spar mill jar, add the 100ml absolute ethyl alcohol again, sealing back is ball-milling medium ball milling 10 hours with the zirconia ball on the roller milling machine, discharging, 80 ℃ of oven dry, 800 ℃ of following preroasts 15 hours, the semi-finished product that obtain were used dry method ball milling 3 hours in the polyurethane ball grinder again, 680 ℃ of following after bakings 10 hours, the back of coming out of the stove was crossed 300 mesh sieves and was promptly got target product then.Record its first reversible specific capacity be 124.6mAh/g, discharge and recharge 300 capacity and keep more than 91%, 300 capacity of high rate performance: 20C discharge keep 85%.
Claims (9)
1, a kind of manganic niobium doping type manganate cathode material for lithium of lithium rechargeable battery is characterized in that: its nominal composition formula is LiMn
2-xNb
xO
4, wherein, doping scope 0＜x＜0.2.
2, the manganic niobium doping type manganate cathode material for lithium of lithium rechargeable battery according to claim 1 is characterized in that: the doping of manganese position is a kind of nominal composition amount in the synthetic doped compound.
3, a kind of method for preparing the manganic niobium doping type manganate cathode material for lithium of the described lithium rechargeable battery of claim 1, it is characterized in that: get lithium compound, manganese compound and niobium compound, mol ratio according to element Li, Mn, Nb is: Li: [(2-x) Mn+xNb]=1: 2 raw materials weighing, wherein 0＜x＜0.2; The raw material that weighs up is added ball mill container, add ball-milling medium and dispersant then, mixing and ball milling 3～10 hours is 50～100 ℃ of oven dry down; Oven dry back powder is at 550～900 ℃ of following preroast 5-20 hours, and the semi-finished product that obtain are used dry method in ball mill ball milling 2-5 hour again, and then at 500～700 ℃ of following after baking 5-20 hours, the back of coming out of the stove is crossed 300 mesh sieves and promptly got target product.
4, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3, it is characterized in that: described dispersant is a kind of in deionized water, industrial alcohol and the absolute ethyl alcohol, or two or three mixture wherein.
5, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3 is characterized in that: ball mill container is a kind of in corundum ball grinder, agate jar, polyurethane ball grinder, the nylon ball grinder.
6, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3 is characterized in that: ball-milling medium is a kind of in zirconia ball, corundum ball, agate ball, the stainless steel ball.
7, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3 is characterized in that: lithium compound is one or both and the two or more mixture in lithium carbonate, lithium oxalate, lithium acetate, the lithium hydroxide.
8, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3, it is characterized in that: described manganese compound is a kind of in electrolytic manganese dioxide, chemical manganese bioxide, the manganese sesquioxide managnic oxide, or two or three mixture.
9, the manganic niobium doping type manganate cathode material for lithium preparation method of lithium rechargeable battery according to claim 3 is characterized in that: described niobium compound is a kind of in niobium hydroxide, niobium pentaoxide, the niobium oxalate.
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|---|---|---|---|
| CN200910020749A CN101540399A (en) | 2009-04-24 | 2009-04-24 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
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| CN200910020749A CN101540399A (en) | 2009-04-24 | 2009-04-24 | Manganic niobium doping type lithium manganate cathode material for lithium-ion secondary battery and preparation method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102779993A (en) * | 2012-07-31 | 2012-11-14 | 临沂杰能新能源材料有限公司 | Lithium ion battery anode material and preparation method |
| CN102916175A (en) * | 2012-10-25 | 2013-02-06 | 湖南长远锂科有限公司 | Lithium manganese oxide spinel of anode materials of lithium ion batteries and method for manufacturing lithium manganese oxide spinel |
| CN106629858A (en) * | 2016-10-10 | 2017-05-10 | 北京化工大学 | Method for removing fine powder in lithium manganate electrode materials in situ |
| CN110085858A (en) * | 2019-05-20 | 2019-08-02 | 山东省科学院能源研究所 | A kind of nickelic tertiary cathode material of niobium-phosphor codoping and its preparation method and application |
| CN112510195A (en) * | 2020-05-25 | 2021-03-16 | 广西富丰矿业有限公司 | Niobium-doped high-compaction high-capacity lithium manganate and preparation method thereof |
| CN113517439A (en) * | 2020-06-30 | 2021-10-19 | 高点(深圳)科技有限公司 | Doped lithium manganate and preparation method and application thereof |
| CN114933333A (en) * | 2022-06-09 | 2022-08-23 | 广西百色市德柳锰业有限公司 | Composite doped modified capacity type lithium manganate and preparation method thereof |
| CN115430432A (en) * | 2022-08-24 | 2022-12-06 | 重庆理工大学 | Oxidation catalyst Li 2 Mn 0.9 Co 0.1 O 3 And method for preparing the same |
-
2009
- 2009-04-24 CN CN200910020749A patent/CN101540399A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102779993A (en) * | 2012-07-31 | 2012-11-14 | 临沂杰能新能源材料有限公司 | Lithium ion battery anode material and preparation method |
| CN102779993B (en) * | 2012-07-31 | 2015-04-08 | 临沂杰能新能源材料有限公司 | Lithium ion battery anode material and preparation method |
| CN102916175A (en) * | 2012-10-25 | 2013-02-06 | 湖南长远锂科有限公司 | Lithium manganese oxide spinel of anode materials of lithium ion batteries and method for manufacturing lithium manganese oxide spinel |
| CN106629858A (en) * | 2016-10-10 | 2017-05-10 | 北京化工大学 | Method for removing fine powder in lithium manganate electrode materials in situ |
| CN110085858A (en) * | 2019-05-20 | 2019-08-02 | 山东省科学院能源研究所 | A kind of nickelic tertiary cathode material of niobium-phosphor codoping and its preparation method and application |
| CN110085858B (en) * | 2019-05-20 | 2020-12-18 | 山东省科学院能源研究所 | Niobium-phosphorus co-doped high-nickel ternary cathode material and preparation method and application thereof |
| CN112510195A (en) * | 2020-05-25 | 2021-03-16 | 广西富丰矿业有限公司 | Niobium-doped high-compaction high-capacity lithium manganate and preparation method thereof |
| CN113517439A (en) * | 2020-06-30 | 2021-10-19 | 高点(深圳)科技有限公司 | Doped lithium manganate and preparation method and application thereof |
| CN114933333A (en) * | 2022-06-09 | 2022-08-23 | 广西百色市德柳锰业有限公司 | Composite doped modified capacity type lithium manganate and preparation method thereof |
| CN115430432A (en) * | 2022-08-24 | 2022-12-06 | 重庆理工大学 | Oxidation catalyst Li 2 Mn 0.9 Co 0.1 O 3 And method for preparing the same |
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Open date: 20090923 |