CN102368545A - Preparation technology of lithium manganate electrode material doping and surface fluoride cladding - Google Patents

Preparation technology of lithium manganate electrode material doping and surface fluoride cladding Download PDF

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CN102368545A
CN102368545A CN2011103363535A CN201110336353A CN102368545A CN 102368545 A CN102368545 A CN 102368545A CN 2011103363535 A CN2011103363535 A CN 2011103363535A CN 201110336353 A CN201110336353 A CN 201110336353A CN 102368545 A CN102368545 A CN 102368545A
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fluoride
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positive electrode
lithium manganate
heat treatment
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陈云贵
孙怀兵
朱丁
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Sichuan University
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Abstract

The invention discloses a modification technology of lithium ion battery electrode material spinel lithium manganate, wherein a layer of fluoride film is cladded on the surface of the lithium manganate after bulk phase doping modification. The method comprises the following steps of: firstly, performing bulk phase doping modification on lithium manganate with a solid phase method; then, cladding a layer of fluoride film on the surface of the modified lithium manganate anode material with a liquid phase method; and performing thermal treatment at 300-600 DEG C in a resistance furnace for 4-10 hours to obtain anode materials of different fluorides and different cladding amounts. The lithium ion battery prepared from the modified lithium ion battery anode material has better circulation performance and high-multiplying power performance at the high temperature of 55 DEG C.

Description

The technology of preparing that a kind of manganic acid lithium electrode material mixes and the surface fluorination thing coats
Technical field
The invention belongs to a kind of through the anode active material of lithium ion battery after the modification, particularly a kind of spinelle LiMn 2- x M x O 4(0 ≦ x≦ 0.1, M is a metallic element) surface coating fluoride electrode material and preparation method thereof.
Background technology
Lithium ion battery (LIB) becomes the optimal selection of power battery of electric vehicle with advantages such as its light weight, energy height and memory-less effects.LiMn 2O 4The theoretical specific capacity of series material is 148 mAh/g; And, overcharging resisting with low cost because of it crossed and put the preferable and environment amenable advantage of performance; And become the focus of current anode material for lithium-ion batteries research; Once becoming the optimal selection of power type LIB, but because it can cause in charge and discharge process material structure to deform (to the cubic phase Li of less stable 2Mn 2O 4Transform, perhaps form Li at material surface 2Mn 2O 4Phase has been stopped up the passage that lithium ion embeds and deviates from), and the Mn in the crystal 3+Disproportionated reaction, the Mn of generation can take place 2+Be dissolved in and make electrode active material loss in the electrolyte, capacity attenuation is very fast, and these make cycle performance, and particularly very poor of high temperature cyclic performance hindered LiMn 2O 4A large amount of commercial applications.Main methods of modification is for coating bulk phase-doped (utilizing divalent or 3 valency elements to replace manganese position and anion replacement oxygen position) and surface at present.At present, the doping of having reported both at home and abroad be coated with:
(1) Co and Li mixing and doping (yellow pine great waves etc., rare metal, 2,006 2)
(2) Co and F mixing and doping (Xiao's table handle etc., Chinese manganese industry, 2,005 4)
(3) Co, Ni, La mixing and doping (Lu Xinghe etc., Hebei Construction Science & Tech. College's journal, 2,005 3)
(4) Al doping (Anbao Yuan etc., Journal of Power Sources 195 (2010) 5032 – 5038)
(5) Li, Cu, Zn, Ni, Co, Fe, Cr, Ga, Al, B and Ti doping (G. Pistoia etc., Chem. Mater. 1997 (9) 1443-1450)
(6) ZrO 2And TiO 2Coat (Kenneth A.Walz etc., Journal of Power Sources 195 (2010) 4943 – 4951)
(7) CeO 2Coat (Hyung-Wook Ha etc., Electrochimica Acta 52 (2007) 3236 – 3241)
(8) MgO coats (J.S. Gnanaraj etc., Electrochemistry Communications 5 (2003) 940 – 945)
(9) Al 2O 3, ZnO and SnO 2Coat (Sung Bin Park etc., Journal of Power Sources 180 (2008) 597 – 601)
(10) LiCoO 2Coat (S.C. Park etc., Journal of Power Sources 130 (2001) 86-92)
(11) anode material for lithium-ion batteries and preparation method thereof, number of patent application: 200310112600.9 Biyadi Co Ltd
(12) a kind of spinelle LiMn 2O 4The surface coats Li 4Ti 5O 12Electrode material and preparation method thereof, number of patent application: 200510020940.8 Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences
Yet; Above doping and coating modification material all have weak point under high temperature circulation; Through the lithium manganate material behind the doping vario-property,, in the charge discharge process, can not effectively suppress the erosion of HF to active material though its structural stability improves; At the oxide coated on surface film; Owing to the reaction of oxidation film and HF is dissolved; Thereby lost the effect of protection active material; In order fundamentally to solve the high-temperature behavior problem of LiMn2O4, we have proposed simultaneously material to be carried out modification from intrinsic structure and surface coating, and clad material is a fluoride stable in HF.
Summary of the invention
To above weak point, the clad material of research is mostly for metal oxide, in the electrochemistry cyclic process before considering; The oxide coating layer can react with electrolyte and lose the effect of guard electrode material; The chemical property of material is affected, and fluoride has stability preferably under bad border of hydrofluoric acid, and fluoride have ionic conductivity preferably; And higher electrochemistry diffusion coefficient is arranged than LiMn2O4; Therefore, the present invention adopts fluoride as clad material, and the LiMn2O4 behind the doping vario-property is carried out surface modification treatment.
The present invention has following characteristics:
(1) the doping vario-property electrode material can not change raw-material structure;
(2) solid phase method doping vario-property electrode material method is simple, and doping is easy to control;
(3) electrode material after the coating does not change the structure of former product;
(4) amount that coats can be controlled through technological parameter flexibly;
(5) raw material of clad material fluoride all is common raw material, and is cheap;
(6) coating process is simple, and flow process is short, easy for industrialized;
(7) electrode material after the coating shows that through electrochemical property test material is the cycle performance of (55 ℃) at high temperature, and high rate performance increases significantly.
Implementation step of the present invention
In the present invention, anode material for lithium-ion batteries is the LiMn after the modification 2- x M x O 4(0 ≦ x≦ 0.1, M is a metallic element) the surface coat one deck and fluoridize material layer and constitute.Described M element can be one or more in the metallic elements such as Li, Cu, Zn, Ni, Co, Fe, Cr, Ga, Al, B, Ti, La, Ce, Pr, Nd, Gd, Sm.Non-fluorine element can be one or more among metal A l, Mg, Zn, Ca, Ba, Sr, La, Ce, Pr, Nd, Er, Y, the Gd in the fluoride; The main effect of above-mentioned doping vario-property is to make LiMn2O4 structure in the electrochemistry cyclic process more stable; And the fluoride that coats is more stable in bad border of HF acid, can stop the corrosiveness of HF acid to positive electrode active materials.Through improving battery cycle performance at high temperature, high rate performance and security performance after the above-mentioned modification.
The preparation method of anode material for lithium-ion batteries of the present invention is earlier to coat processing with the LiMn2O4 surface of liquid phase method after to doping vario-property.The surface coats the fluoride layer positive electrode need obtain anode material for lithium ion battery at 300-600 ℃ of heat treatment 4-10 h.Heat treated purpose mainly is to make the formation that coating layer can be stable.
The assembling of battery:
With positive active material and the binding agent (PVDF) after grinding; Conductive agent (acetylene black) is placed on agate by the mixed of 8.5:1:0.5 and grinds in the alms bowl and grind; After being mixed, it pours in the beaker; Drip an amount of NMP (N-methyl pyrrolidone), place it in the ultrasonic dispersing appearance and evenly disperse, and constantly stir with glass bar.Uniformly be coated in aluminium foil on applicator the slurry that mixes; Thickness is 20mm, puts into the dry 12h of vacuum drying chamber, then compressing tablet and the anodal disk that is washed into f=14mm; In glove box with metal lithium sheet as negative pole; The Celgard2400 polypropylene porous film is a barrier film, uses EC+DEC+DMC (volume ratio 1:1:1) to be solvent, 1.0M LiPF 6Be the organic electrolyte of solute, and the positive plate for preparing is assembled into half-cell.
Performance test
Charge and discharge cycles be battery 55 ℃ of temperature, voltage 3-4.3 V, current density is to carry out charge-discharge test under 1 C (147 mA).High rate performance adopts current density range to test for 1-15 C.
The explanation of accompanying drawing table:
Fig. 1 is 55 ℃ of cycle performances of high temperature of Comparative Examples 1 and Comparative Examples 2
Fig. 2 is the initial charge/discharge curve of the positive electrode that makes of embodiment 1,2,3 and Comparative Examples 1.
Fig. 3 is the cycle performance of the positive electrode that makes of embodiment 1,2,3 Comparative Examples 1.
Fig. 4 is the high rate performance of the positive electrode that makes of embodiment 1,2,3 Comparative Examples 1.
Fig. 5 is the initial charge/discharge curve of the positive electrode that makes of embodiment 4,5,6 Comparative Examples 1.
Fig. 6 is the cycle performance of the positive electrode that makes of embodiment 4,5,6 Comparative Examples 1.
Fig. 7 is the high rate performance of the positive electrode that makes of embodiment 4,5,6 Comparative Examples 1.
The Electrochemical results of material gathers sees table 1.
Further specify the present invention with embodiment below.
Comparative Examples 1: the preparation of positive electrode: in Li/Mn/Cr mol ratio (1 ~ 1.1): the ratio of 1.99:0.01 is with Li 2CO 3, MnO 2And Cr 2O 3Mix the manganate cathode material for lithium of back after 750 ℃ of heat treatment 15h obtain 3g doping material as a comparison.
Comparative Examples 2: in Li/Mn mol ratio (1 ~ 1.1): 2 ratio is with Li 2CO 3And MnO 2Mix the back and obtain 3g manganate cathode material for lithium material as a comparison at 750 ℃ of heat treatment 15h.
As can beappreciated from fig. 1, with respect to the manganate cathode material for lithium (Comparative Examples 2) of the Cr that do not mix, the cyclical stability that the high temperature of the manganate cathode material for lithium of doping Cr (Comparative Examples 1) is 55 ℃ will be got well a lot.
Embodiment 1: the preparation of positive electrode: in Li/Mn/Cr mol ratio 1-1.1: 1.99: 0.01 ratio is with Li 2CO 3, MnO 2And Cr 2O 3Mix the back and obtain the manganate cathode material for lithium after 3g mixes at 750 ℃ of heat treatment 15h.The 3g active material is joined 0.0335g La (NO 3) 3In the aqueous solution, at room temperature stir 3h, dropwise add 0.0090gNH then 4The F aqueous solution, filtration drying after stirring 3h under 80 ℃ at 500 ℃ of following heat treatment 6h, gets the material that obtains to coat LaF to the end 3Positive electrode for active material 0.5 weight %.
Embodiment 2: except with La (NO 3) 3Quality change 0.0669g into, NH 4The quality of F changes into outside the 0.0175g, and all the other are identical with embodiment 1, gets to coat LaF to the end 3Positive electrode for active material 1.0 weight %.
Except with La (NO 3) 3Quality change 0.1338g into, NH 4The quality of F changes into outside the 0.0358g, and all the other are identical with embodiment 1, gets to coat LaF to the end 3Positive electrode for active material 2.0 weight %.
On Comparative Examples 1 basis of doping Cr, coat LaF 3The discharge capacity of embodiment 1, embodiment 2 and embodiment 3 certain reduction (Fig. 2) is arranged, but the cyclical stability of 55 ℃ of high temperature and high rate capability have more significantly and improve (Fig. 3 and Fig. 4).
Embodiment 4 is except with 0.0335g La (NO 3) 3Change 0.0255gSr (NO into 3) 2, 0.0090gNH 4F changes 0.0092gNH into 4Outside the F, remaining is identical with embodiment 1, gets to coat SrF to the end 2Positive electrode for active material 0.5 weight %.
Embodiment 5 is except with Sr (NO 3) 2Quality change 0.0511g into, NH 4The quality of F changes into outside the 0.0184g, and remaining is identical with embodiment 4, gets to coat SrF to the end 2Positive electrode for active material 1.0 weight %.
Embodiment 6 is except with Sr (NO 3) 2Quality change 0.1021g into, the quality of NH4F changes into outside the 0.0369g, remaining is identical with embodiment 4, coat SrF to the end 2Positive electrode for active material 2.0 weight %.
On Comparative Examples 1 basis of doping Cr, coat SrF 2The discharge capacity of embodiment 4, embodiment 5 and embodiment 6 do not see significant change (Fig. 5), but the cyclical stability of 55 ℃ of high temperature has clear improvement (Fig. 6), coats 1.0% SrF 2The high rate capability of embodiment 5 also have more significantly and improve (Fig. 7).
Table 1 gathers above-mentioned experimental result, can find out simultaneously, on Comparative Examples 1 basis of doping Cr, coats LaF 3With coating SrF 2The charge transfer resistance of all embodiment all obviously reduce.
Table 1.
Figure 207119DEST_PATH_IMAGE001
aMaterial is at 55 ℃, the initial discharge capacity of 1C charge and discharge cycles.
bMaterial is at 55 ℃, the capability retention after the 1C charge and discharge cycles 100 times.
cWith respect to the capacity ratio of material under the 1C current cycle.
dCompletely fill the charge transfer resistance after the circulation for the first time under the attitude.
eCompletely fill attitude following 100 times the circulation after charge transfer resistance.

Claims (9)

1. spinel lithium manganate coats the fluoride positive electrode, it is characterized in that: described spinel lithium manganate is through the positive electrode LiMn after bulk phase-doped modified 2- x M x O 4(0 ≦ x≦ 0.1, M is a metallic element), and coat one deck fluoride films on the surface.
2. the positive electrode of the doping vario-property that requires like right 1 is characterized in that: LiMn 2- x M x O 4Middle M element can be one or more in the metallic elements such as Li, Cu, Zn, Ni, Co, Fe, Cr, Ga, Al, B, Ti, La, Ce, Pr, Nd, Gd, Sm.
3. the doping vario-property spinel lithium manganate that requires like right 1 coats the fluoride positive electrode, and it is characterized in that: the amount of said fluoride is the 0.01-10 weight % of positive electrode.
4. the fluoride that requires like right 3, it is characterized in that: non-fluorine element is one or more among Al, Mg, Zn, Ca, Ba, Sr, La, Ce, Pr, Nd, Er, Y, the Gd in the described fluoride.
5. the preparation method of the doping vario-property spinel lithium manganate that requires like right 3 may further comprise the steps: a, with MnO 2, Li 2CO 3Evenly mix by stoichiometric proportion with oxide that contains the M metallic element or salt; B, with the mixture of above-mentioned a gained at 700-900 ℃ of following heat treatment 10-20h.
6. the M metallic salt that requires like right 5 is characterized in that: salt can be a kind of in nitric acid, carbonic acid, the sulfate.
7. the fluoride coating preparation method of the positive electrode that requires like right 3 may further comprise the steps: a, with NH 4F and manganate cathode material for lithium are put into the aqueous solution and are evenly mixed, and at room temperature stir 4-10 h, and the salting liquid with non-fluorine element in the fluoride dropwise adds in the mixed solution then, stir 4-10 h down at 50-80 ℃; B, the mixture filtration of above-mentioned a gained is back at 80-120 ℃ of following dry 5-20 h then at 300-600 ℃ of heat treatment 4-10 h, obtains anode material for lithium ion battery.
8. the non-fluorine element salting liquid that requires like right 7 is characterized in that: said non-fluorine element salting liquid can be a kind of in nitric acid, sulfuric acid, the solution of chlorate.
9. the heat treatment that requires like right 7, it is characterized in that: said heat treatment can be under atmospheric environment, carries out under argon shield or the nitrogen protection.
CN2011103363535A 2011-10-31 2011-10-31 Preparation technology of lithium manganate electrode material doping and surface fluoride cladding Pending CN102368545A (en)

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Cited By (14)

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CN103022502A (en) * 2012-12-19 2013-04-03 天津巴莫科技股份有限公司 Compounding and coating method of anode material for lithium ion cell
CN104409722A (en) * 2014-12-17 2015-03-11 湖南杉杉新能源有限公司 Method for improving performance of lithium manganate cathode material
CN104521040A (en) * 2012-11-06 2015-04-15 株式会社Lg化学 Cathode active material for secondary battery and secondary battery comprising same
CN104518213A (en) * 2013-09-26 2015-04-15 天津通一新能源科技有限公司 Synthesis method of poly lithium manganate material
CN105917514A (en) * 2014-01-14 2016-08-31 昭和电工株式会社 Lithium secondary battery and conductive assistant used in same
CN106972153A (en) * 2016-01-13 2017-07-21 云南民族大学 The composite mixed type manganate cathode material for lithium of a kind of low lithium, copper content and preparation method
CN111416122A (en) * 2020-03-23 2020-07-14 上海电力大学 Coating modified high-nickel cathode material and preparation method thereof
CN111868977A (en) * 2018-05-25 2020-10-30 本田技研工业株式会社 Composite electrode material for fluoride ion electrochemical cells
CN112002900A (en) * 2020-08-12 2020-11-27 新乡市中天新能源科技股份有限公司 High-rate positive electrode material, preparation method thereof and non-aqueous energy storage device
CN112151798A (en) * 2020-09-16 2020-12-29 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
CN112919554A (en) * 2021-05-11 2021-06-08 蜂巢能源科技有限公司 Fluorine-doped lithium cathode material and preparation method and application thereof
CN113437300A (en) * 2021-06-28 2021-09-24 山东大学 Polyvinylidene fluoride modified lithium manganate positive electrode material and preparation method thereof
CN114284483A (en) * 2021-12-24 2022-04-05 安徽博石高科新材料股份有限公司 Preparation and application of zirconium dioxide-coated lithium manganate cathode material
CN115084487A (en) * 2022-08-01 2022-09-20 上海兰钧新能源科技有限公司 Electrode material preparation method and electrode material

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CN101156260A (en) * 2005-04-15 2008-04-02 能原材公司 Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same

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CN101156260A (en) * 2005-04-15 2008-04-02 能原材公司 Cathode active material coated with fluorine compound for lithium secondary batteries and method for preparing the same
CN101038965A (en) * 2006-03-14 2007-09-19 深圳市比克电池有限公司 Method for preparing modified spinelle manganic acid lithium material and lithium secondary battery

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CN104521040A (en) * 2012-11-06 2015-04-15 株式会社Lg化学 Cathode active material for secondary battery and secondary battery comprising same
CN103022502A (en) * 2012-12-19 2013-04-03 天津巴莫科技股份有限公司 Compounding and coating method of anode material for lithium ion cell
CN104518213A (en) * 2013-09-26 2015-04-15 天津通一新能源科技有限公司 Synthesis method of poly lithium manganate material
CN105917514A (en) * 2014-01-14 2016-08-31 昭和电工株式会社 Lithium secondary battery and conductive assistant used in same
CN104409722A (en) * 2014-12-17 2015-03-11 湖南杉杉新能源有限公司 Method for improving performance of lithium manganate cathode material
CN104409722B (en) * 2014-12-17 2017-02-22 湖南杉杉新能源有限公司 Method for improving performance of lithium manganate cathode material
CN106972153A (en) * 2016-01-13 2017-07-21 云南民族大学 The composite mixed type manganate cathode material for lithium of a kind of low lithium, copper content and preparation method
CN111868977A (en) * 2018-05-25 2020-10-30 本田技研工业株式会社 Composite electrode material for fluoride ion electrochemical cells
CN111416122A (en) * 2020-03-23 2020-07-14 上海电力大学 Coating modified high-nickel cathode material and preparation method thereof
CN111416122B (en) * 2020-03-23 2023-04-28 上海电力大学 Coated modified high-nickel positive electrode material and preparation method thereof
CN112002900A (en) * 2020-08-12 2020-11-27 新乡市中天新能源科技股份有限公司 High-rate positive electrode material, preparation method thereof and non-aqueous energy storage device
CN112151798A (en) * 2020-09-16 2020-12-29 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
CN112151798B (en) * 2020-09-16 2022-03-15 天目湖先进储能技术研究院有限公司 Fluoride/oxide co-coated positive electrode material and preparation method thereof
CN112919554A (en) * 2021-05-11 2021-06-08 蜂巢能源科技有限公司 Fluorine-doped lithium cathode material and preparation method and application thereof
CN112919554B (en) * 2021-05-11 2021-10-15 蜂巢能源科技有限公司 Fluorine-doped lithium cathode material and preparation method and application thereof
WO2022237110A1 (en) * 2021-05-11 2022-11-17 蜂巢能源科技有限公司 Fluorine-doped lithium positive electrode material, preparation method therefor and use thereof
CN113437300A (en) * 2021-06-28 2021-09-24 山东大学 Polyvinylidene fluoride modified lithium manganate positive electrode material and preparation method thereof
CN114284483A (en) * 2021-12-24 2022-04-05 安徽博石高科新材料股份有限公司 Preparation and application of zirconium dioxide-coated lithium manganate cathode material
CN115084487A (en) * 2022-08-01 2022-09-20 上海兰钧新能源科技有限公司 Electrode material preparation method and electrode material

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Application publication date: 20120307