CN1744353A - The preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries - Google Patents

The preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries Download PDF

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CN1744353A
CN1744353A CNA2004100753712A CN200410075371A CN1744353A CN 1744353 A CN1744353 A CN 1744353A CN A2004100753712 A CNA2004100753712 A CN A2004100753712A CN 200410075371 A CN200410075371 A CN 200410075371A CN 1744353 A CN1744353 A CN 1744353A
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lithium
ion batteries
anode material
preparation
spherical
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CN100355121C (en
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周园
马培华
冉广芬
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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    • Y02E60/10—Energy storage using batteries

Abstract

The present invention relates to a kind of preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries, this method at first is to utilize special low-temperature electrolytic technology to produce spherical pure or compound M metal oxide MnO 2Particulate is introduced lithium ion by molten (melting) diffusion process then, gets spinelle LiM through thermal response xMn 2-xO 4Positive electrode; The spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries of method of the present invention preparation is different from obtained multiaspect class columnar materials such as the conventional solid-state method now reported, firing method, molten (melting) liquid infusion process, coprecipitation, sol-gel process, emulsion-seasoning, template, hydro thermal method, because sphere is the shape of unit volume external surface area minimum in the space geometry shape, the spherical cathode material reduces the surface area that positive electrode is exposed to electrolyte solution greatly, avoid most advanced and sophisticated active effect, suppressed Mn 2+The decomposition of dissolving loss and electrolyte, thus improve and raising LiMn 2O 4The positive electrode performance, and can improve the battery pole piece combination property greatly.

Description

The preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries
Technical field
The present invention relates to a kind of preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries.
Background technology
The energy, material and information are three big pillars of the human society survival and development, and human society will be realized the strategy of sustainable development, must develop new material and new energy technology, conservation of nature ENVIRONMENT AND NATURAL RESOURCES.Along with the develop rapidly of modern electronic technology, electronic apparatus constantly to miniaturization, lightweight and the fast development of high performance direction, adds the continuous enhancing of people's environmental consciousness, presses for to develop green power supply environmentally friendly, excellent performance simultaneously.And the lithium ion battery that the nearly more than ten years become worldwide upsurge satisfies one of optimal energy of these requirements beyond doubt.Compare with traditional secondary cell such as lead-acid battery, Cd-Ni battery, Ni-MH battery, aspect specific power, specific energy density and the charge-discharge performance remarkable advantages is being arranged.At present, lithium ion battery has been widely used in mobile phone, notebook computer, has taken the photograph and put camera, household electrical appliance, UPS, space technology, national defense industry etc.Along with the fuel oil transport facility is extensive use of, caused CO in the global atmosphere 2The increase of content and cause " greenhouse effect " and city environmental pollution.At present, national governments have paid much attention to this problem, electric automobile promote the use of the optimal path that is considered to finally address this problem, and lithium ion battery becomes the best energy of electric automobile.Extremely tempting market prospects make countries in the world all fall over each other to research and develop lithium ion battery.All there is the medium-term and long-term research program of oneself in Japan, the U.S., Europe, as " the LIBES plan " of Japan, and " the LIBEVA plan " in " the USABC plan " of the U.S. and Europe and " joule plan ".China also lists lithium ion battery in " 95 ", " 15 " key research projects and " 863 " high-tech project input huge fund and researches and develops.
The essence of lithium rechargeable battery reaction is a Li +Ion concentration cell: during charging, Li +Ion is deviate from from the positive polarization compound and is embedded the negative pole lattice, and positive pole is in poor lithium attitude; During discharge, Li +Ion from negative pole deviate from and insert anodal, just very rich lithium attitude.For keeping the balance of electric charge, the electronics that equal number is arranged in the charge and discharge process is through the external circuit transmission, with Li +Ion moves between both positive and negative polarity together, makes both positive and negative polarity generation redox reaction, keeps certain current potential.The chemical property and the Li of the positive and negative electrode intercalation compounds of operating potential and formation battery +Ion concentration is relevant.
Lithium ion secondary battery anode material mainly is embedding lithium transition-metal oxide LiCoO 2, LiNiO 2, LiMn 2O 4And modified compound, present commercial positive electrode mainly is LiCoO 2, but LiCoO 2Fatal shortcoming is that the cobalt resource reserves are limited, costs an arm and a leg, and manufacturing cost is too high and can't use in large-sized battery (as EV, HEV), and Co is poisonous element, can cause environmental pollution, and therefore, the substitute products of seeking cobalt acid lithium have become inevitable.LiNiO 2Though than LiCoO 2Have that cost is low, energy advantages of higher and become a kind of positive electrode of very attractive, but its shortcoming is: the influence of irreversible phase change when at first its reversible capacity is subjected to that lithium takes off embedding for the first time, capacitance loss is big; Next LiNiO in cyclic process 2Structure easily change and NiO 2Stability compare CoO 2Also poor, thermal decomposition easily takes place, produce oxygen, thereby its safety problem is the focus of common concern, aspect preparation, also have any problem in addition.LiMn 2O 4Advantage is: 1) manganese aboundresources, and especially China's manganese resource reserve occupies first of the countries in the world; 2) low price; 3) nontoxic, pollute little; 4) with spinelle phase LiMn 2O 4Material is as the lithium ion battery operating voltage height of positive pole assembling, and fail safe is good, and is with low cost; 5) owing to be extensive use of in primary cell, battery industry is easy to accept, and the recycling problem solved already substantially.So spinelle phase LiMn 2O 4Be considered to LiCoO 2Best substitution material.
But spinelle phase LiMn 2O 4Positive electrode can't influence LiMn accepts by lithium ion battery industry fully at present 2O 4The key factor of performance mainly contains 4 points, i.e. the crystal structure phase transformation, the Mn that cause of Jahn-Teller effect 2+Dissolving loss, the decomposition of electrolyte and the formation of passivating film, even under high temperature (＞55 ℃) condition, LiMn 2O 4The too fast reason of positive electrode capacity attenuation also is because Jahn-Telle: effect, Mn 2+The result that dissolving and surface passivation more seriously cause.Improve at present and raising LiMn 2O 4The main method of positive electrode performance, they or single bulk phase-doped or pure surface coat.Though bulk phase-doped is to study morely at present improving on the positive electrode performance, but electrode material will be exposed in the electrolyte solution inevitably in lithium ion battery, thereby the dissolving loss of essential element is another key factor that influences material property in the positive electrode, particularly to LiMn 2O 4The spinelle positive electrode is all the more so, and the surface coats one of effective ways that can address this problem beyond doubt.
Because sphere is the shape of unit volume external surface area minimum in the space geometry shape, positive electrode is made sphere will reduce the surface area that positive electrode is exposed to electrolyte solution greatly undoubtedly, and a large amount of projections that exist in positive electrode surface of present preparation have been eliminated substantially, to avoid most advanced and sophisticated active effect, suppress Mn on certain meaning 2+The decomposition of dissolving loss and electrolyte, thus improve and raising LiMn 2O 4The positive electrode performance, and can improve the battery pole piece combination property greatly.
Summary of the invention
Preparation method of the present invention utilizes special low-temperature electrolytic technology to produce spherical pure or compound M metal oxide MnO 2Particulate is introduced lithium ion by molten (melting) diffusion process then, gets spinelle LiM through thermal response XMn 2-XO 4Positive electrode.The spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries of this method preparation is different from obtained polygonal prism columnar materials such as the conventional solid-state method now reported, firing method, molten (melting) liquid infusion process, coprecipitation, sol-gel process, emulsion-seasoning, template, hydro thermal method, because sphere is the shape of unit volume external surface area minimum in the space geometry shape, the spherical cathode material has reduced the surface area that positive electrode is exposed to electrolyte solution greatly, avoid most advanced and sophisticated active effect, suppressed Mn 2The decomposition of+dissolving loss and electrolyte, thus improve and raising LiMn 2O 4The positive electrode performance, and can improve the battery pole piece combination property greatly.
For achieving the above object, the invention provides a kind of preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries, this method comprises the steps:
A kind of preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries, wherein this method comprises the steps:
(1) be under-25 ℃-+25 ℃ in temperature, electrolysis Mn salt or the Mn salt that contains doped chemical M are produced spherical MnO 2Particulate or compound M metal oxide MnO 2Particulate, wherein doped chemical M is selected from a kind of among Co, Ni, Cr, Fe, Al, Zn, the Cu;
(2) with the MnO that produces in the step (1) 2Particulate or compound M metal oxide MnO 2Particulate is pressed LiM XMn 2-XO 4Mol ratio 1: x: (2-x), add in lithium salt solution or the fused salt; Introduce lithium ion by molten (melting) diffusion process, make LiM XMn 2-XO 4Wet micro mist, wherein x=0～0.3;
(3) be 20～80 ℃ of following vacuumizes with the wet micro mist of step (2) gained in temperature;
(4) the dried micro mist of step (3) gained was prepared spinelle LiM in synthetic 4～20 hours in 350～580 ℃ of low-temperature bakes XMn 2-XO 4Material;
(5) material that step (4) is synthetic in 700～900 ℃ of high-temperature roasting crystallizations got final product in 2～10 hours the anodal LiM of spherical spinel XMn 2-XO 4Anode material for lithium-ion batteries.
The electrolytic current density 0-1A/cm of described step (1) 2
Mn salt in the described step (1) is selected from least a in the nitrate, sulfate, acetate, chloride of Mn.
Doped chemical M raw material in the described step (1) is at least a in the nitrate, sulfate, acetate, chloride of Co, Ni, Cr, Fe, Al, Zn, Cu.
Described step (2) lithium salts is selected from the solution or the fused salt of at least a lithium compound in lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate and the lithium citrate.
The step that molten (melting) diffusion process in the described step (2) is introduced lithium ion comprises MnO 2Particulate or compound M metal oxide MnO 2Particulate added in the lithium salt solution dipping diffusion 2～10 hours, or joined in 280-380 ℃ the lithium salts fused salt insulation diffusion 2～10 hours.
This method also can be used for spherical stratiform LiM yCo 1-yO 2With the synthetic preparation of Li-V-Oxide anode material for lithium-ion batteries, wherein M is selected from Co, Ni, Mn, y=0～1.
The present invention has following advantage compared to existing technology:
Adopt spherical spinel Li-Mn-Oxide material to reduce the surface area that positive electrode is exposed to electrolyte solution, eliminated positive electrode surface a large amount of projections that exist of present preparation substantially, will avoid most advanced and sophisticated active effect, suppress Mn on certain meaning 2+The decomposition of dissolving loss and electrolyte, thus improve and raising LiMn 2O 4The positive electrode performance, and can improve the battery pole piece combination property greatly.
Description of drawings
Fig. 1 is a spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries preparation technology flow chart;
Fig. 2 is for utilizing spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries of the present invention
Fig. 3 is for utilizing the prismatic strong spinelle Li-Mn-Oxide anode material for lithium-ion batteries of conventional multiaspect;
Fig. 4 is the anodal LiMn of the spherical spinel that adopts the inventive method preparation 2O 4Anode material for lithium-ion batteries X-ray powder diffraction figure.
Can see relatively that by Fig. 2 and Fig. 3 utilizing spinelle Li-Mn-Oxide material pattern of the present invention to be different from fully utilizes conventional spinelle Li-Mn-Oxide material, the inventive method spinelle Li-Mn-Oxide material is spherical substantially, and conventional spinelle Li-Mn-Oxide material is the polygonal prism column, and its surface includes many seamed edges and convex angular point;
Fig. 4 illustrates that the spherical Li-Mn-Oxide material of the inventive method preparation is pure spinelle phase material.
Embodiment
Embodiment: the anodal LiMn of spherical spinel 2O 4Anode material for lithium-ion batteries and preparation thereof
With reference to Fig. 1, analyze pure MnSO by the 1.5M of 900mL 4Adding the 100mL volume by volume concentration in the solution is the pure H of 97% analysis 2SO 4Solution composition electrolyte, notes are added to inner portion to be had in the electrolytic cell of circulating cooling pipe, adopts stereotype to do electrode, and the anode effective area is 150cm 2, control electrolytic cell temperature is 20 ℃, Faradaic current is 25A/cm 2, low-temperature electrolytic is produced spherical MnO 2Particulate; The micro mist that the last step makes is put in 310 ℃ of lithium nitrate fused salts, cooled off fused salt behind the insulation diffusion 3h, use deionized water flush away surface lithium nitrate afterwards; The wet micro mist of gained is 40 ℃ of following vacuumizes in temperature, and the dried micro mist of gained made spinelle LiMn in synthetic 10 hours in 520 ℃ of low temperature 2O 4Material, at last with synthetic material in 760 ℃ of high temperature crystallizations got final product in 6 hours the anodal LiMn of spherical spinel 2O 4Anode material for lithium-ion batteries.

Claims (7)

1, a kind of preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries, wherein this method comprises the steps:
(1) be under-25 ℃-+25 ℃ in temperature, electrolysis Mn salt or the Mn salt that contains doped chemical M are produced spherical MnO 2Particulate or compound M metal oxide MnO 2Particulate, wherein doped chemical M is selected from a kind of among Co, Ni, Cr, Fe, Al, Zn, the Cu;
(2) with the MnO that produces in the step (1) 2Particulate or compound M metal oxide MnO 2Particulate is pressed LiM XMn 2-XO 4Mol ratio 1: x: (2-x), add in lithium salt solution or the fused salt; Introduce lithium ion by molten (melting) diffusion process, make LiM XMn 2-XO 4Wet micro mist, wherein x=0～0.3;
(3) be 20～80 ℃ of following vacuumizes with the wet micro mist of step (2) gained in temperature;
(4) the dried micro mist of step (3) gained was prepared spinelle LiM in synthetic 4～20 hours in 350～580 ℃ of low-temperature bakes XMn 2-XO 4Material;
(5) material that step (4) is synthetic in 700～900 ℃ of high-temperature roasting crystallizations got final product in 2～10 hours the anodal LiM of spherical spinel XMn 2-XO 4Anode material for lithium-ion batteries.
2, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that the electrolytic current density 0-1A/cm of described step (1) 2
3, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that the Mn salt in the described step (1) is selected from least a in the nitrate of Mn, sulfate, acetate, the chloride.
4, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that doped chemical M raw material in the described step (1) is at least a in the nitrate, sulfate, acetate, chloride of Co, Ni, Cr, Fe, Al, Zn, Cu.
5, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that described step (2) lithium salts is selected from the solution or the fused salt of at least a lithium compound in lithium nitrate, lithium carbonate, lithium hydroxide, lithium acetate and the lithium citrate.
6, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that the step of molten (melting) diffusion process introducing lithium ion in the described step (2) comprises MnO 2Particulate or compound M metal oxide MnO 2Particulate added in the lithium salt solution dipping diffusion 2～10 hours, or joined in 280-380 ℃ the lithium salts fused salt insulation diffusion 2～10 hours.
7, the preparation method of spherical spinel Li-Mn-Oxide anode material for lithium-ion batteries as claimed in claim 1 is characterized in that this method also can be used for spherical stratiform LiM yCo 1-yO 2With the synthetic preparation of Li-V-Oxide anode material for lithium-ion batteries, wherein M is selected from Co, Ni, Mn, y=0～1.
CNB2004100753712A 2004-08-31 2004-08-31 Method for preparnig spherical spinel Li-Mn-oxide lithium ion cell anode material Expired - Fee Related CN100355121C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100479921C (en) * 2006-06-30 2009-04-22 北京化工大学 Sphericity spinel material with cage construction and method for preparing the same
CN101355161B (en) * 2008-09-17 2011-09-28 长沙矿冶研究院 Method for preparing lithium ion battery anode material nickel cobalt lithium manganate
CN103000873A (en) * 2012-10-09 2013-03-27 江苏科捷锂电池有限公司 Method for preparing lithium manganese oxide spinel anode material through molten-salt growth method
CN105226265A (en) * 2014-06-20 2016-01-06 吕传盛 Be suitable for siliceous biphasic powder and the manufacture method thereof of cathode materials for lithium battery
CN106784788A (en) * 2016-12-23 2017-05-31 安徽工业大学 One kind prepares porous LiMn by template of carbon ball2O4Method
CN108147467A (en) * 2017-12-25 2018-06-12 北京理工大学 The preparation method of ultra-thin two-dimension pattern nanometer sheet multilevel hierarchy manganate cathode material for lithium

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CN105439206B (en) * 2015-11-10 2017-04-19 西安交通大学 Method for preparing manganese-based lithium ion battery positive electrode material based on alkali metal-liquid ammonia process

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CN1100355C (en) * 1999-07-28 2003-01-29 北京大陆太极电池有限公司 Process for preparing positive electrode material LiCrxMn2-xO4 of secondary lithium battery by solid state method
JP2002251995A (en) * 2000-12-22 2002-09-06 Mitsui Mining & Smelting Co Ltd Spinel type positive electrode material for lithium secondary battery and manufacturing method
JP2002260654A (en) * 2000-12-28 2002-09-13 Mitsui Mining & Smelting Co Ltd Spinel-type positive electrode material for lithium secondary battery, and its manufacturing method
CN1297020C (en) * 2002-12-24 2007-01-24 中国科学院青海盐湖研究所 Calicining process for high-quality lithium ion battery positive electrodes and calcining apparatus thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100479921C (en) * 2006-06-30 2009-04-22 北京化工大学 Sphericity spinel material with cage construction and method for preparing the same
CN101355161B (en) * 2008-09-17 2011-09-28 长沙矿冶研究院 Method for preparing lithium ion battery anode material nickel cobalt lithium manganate
CN103000873A (en) * 2012-10-09 2013-03-27 江苏科捷锂电池有限公司 Method for preparing lithium manganese oxide spinel anode material through molten-salt growth method
CN105226265A (en) * 2014-06-20 2016-01-06 吕传盛 Be suitable for siliceous biphasic powder and the manufacture method thereof of cathode materials for lithium battery
CN105226265B (en) * 2014-06-20 2018-01-19 吕传盛 It is applicable the siliceous biphasic powder and its manufacture method of cathode materials for lithium battery
CN106784788A (en) * 2016-12-23 2017-05-31 安徽工业大学 One kind prepares porous LiMn by template of carbon ball2O4Method
CN108147467A (en) * 2017-12-25 2018-06-12 北京理工大学 The preparation method of ultra-thin two-dimension pattern nanometer sheet multilevel hierarchy manganate cathode material for lithium

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