CN102306762A - Lithium ion battery cathode material and preparation method thereof - Google Patents

Lithium ion battery cathode material and preparation method thereof Download PDF

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Publication number
CN102306762A
CN102306762A CN201110275835A CN201110275835A CN102306762A CN 102306762 A CN102306762 A CN 102306762A CN 201110275835 A CN201110275835 A CN 201110275835A CN 201110275835 A CN201110275835 A CN 201110275835A CN 102306762 A CN102306762 A CN 102306762A
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China
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lithium
lt
preparation method
kind
compound
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CN201110275835A
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Chinese (zh)
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孙学磊
张永胜
王宗衡
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河南捷和新能源材料有限公司
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Publication of CN102306762A publication Critical patent/CN102306762A/en

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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50Manufacturing or production processes characterised by the final manufactured product
    • Y02P70/54Manufacturing of lithium-ion, lead-acid or alkaline secondary batteries

Abstract

The invention discloses a lithium ion battery cathode material and a preparation method thereof. The technical scheme of the invention is that: the material provided by the invention is represented by a chemical formula of: xLi[Li1/3Mn2/3-aTia]O2-(1-x)Li[Mn1-b-cCrbMc]O2, wherein 0<x<1, 0.04<=a<=0.1, 0.06<=b<=0.6, 0<=c<=0.3, and M is one or two selected from Fe, Ni, and Zn. The material has a layered crystal structure. The preparation method comprises steps that: compounds of lithium, manganese, titanium, chromium, and M are weighed according to an element molar ratio of (1+0.33x):[1-b-c-(0.33+a-b-c)x]:ax:b(1-x):c(1-x); the materials are sufficiently mixed by ball-milling in a ball mill filled with an appropriate amount of a solvent medium; the obtained mixture is dried by baking, and is roasted under a high temperature in an electric resistance furnace; the mixture is then cooled to room temperature. The raw materials adopted in the invention are cheap and easy to obtain. The preparation method is easy to operate and to control. The obtained product has high tap-density and stable properties. Therefore, the material and the method are suitable for industrialized productions.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof

Technical field:

The present invention relates to anode material for lithium-ion batteries, particularly anode material for lithium-ion batteries of a kind of layered crystal structure of high power capacity and preparation method thereof.

Background technology:

Lithium ion battery has that voltage height, volume are little, memory-less effect, plurality of advantages such as have extended cycle life, since earlier 1990s is born, and extensive use on portable type electronic products such as mobile phone, notebook computer, digital camera.But the positive electrode that uses in these batteries mainly is cobalt acid lithium (LiCoO 2), since cobalt resource rare with cost an arm and a leg, and cobalt acid lithium exists not enoughly at aspects such as fail safe, cycle lives, press for the new positive electrode of exploitation and substitute cobalt acid lithium.The LiNiO that has layered crystal structure equally 2Capacity is higher and price is lower, but preparation condition is harsh, and stability and poor stability are difficult to apply; Stratiform LiMnO 2Also structural instability.Spinel structure LiMn 2O 4With olivine structural LiFePO 4All have advantages such as raw material sources are abundant, fail safe is good, being expected to be used to make large-scale lithium ion battery and being electric automobile provides power or is used for energy storage, still also all comes with some shortcomings.LiMn 2O 4Specific capacity is lower, and the cycle performance especially cycle performance under the high temperature is poor.LiFePO 4Voltage is lower, and powder density is little, and high current charge-discharge and cryogenic property are relatively poor.

In recent years, rich lithium stratiform solid solution system has received researcher's broad research as the positive electrode of one type of novel height ratio capacity, can be used as a kind of new material of anode material for lithium-ion batteries.

Summary of the invention:

The object of the present invention is to provide a kind of function admirable and low cost of manufacture, be fit to anode material for lithium-ion batteries of industrial applications and preparation method thereof.

Technical scheme of the present invention is that a kind of anode material for lithium-ion batteries is characterized in that: chemical formula is xLi [Li 1/3Mn 2/3-aTi a] O 2-(1-x) Li [Mn 1-b-cCr bM c] O 2, wherein, 0<x<1,0.04≤a≤0.1,0.06≤b≤0.6,0≤c≤0.3, M is one or both among Fe, Ni, the Zn, and this material has the crystal structure of stratiform.A kind of preparation method of anode material for lithium-ion batteries; It is characterized in that: the compound of lithium, manganese, titanium, chromium, M is (1+0.33x) by the element mol ratio: [1-b-c-(0.33+a-b-c) x]: ax: b (1-x): c (1-x) weighs; Abundant ball mill mixing in being added with the ball mill of an amount of solvent medium; Gained mixture oven dry back high-temperature roasting in resistance furnace is cooled to room temperature then.The compound of said lithium is a kind of in lithium carbonate, the lithium hydroxide; The compound of manganese is a kind of in manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, the manganese carbonate; The compound of titanium is a titanium dioxide; The compound of chromium is a kind of in chrome green, the chromium trioxide; The compound that contains M is one or both in iron oxide, nickel oxide, the zinc oxide.The time of said mechanical milling process is 1 ~ 20h, and solvent medium is water, alcohol or the mixture of the two.Said drying course carries out under 50 ~ 120 ℃ temperature.The temperature of said high-temperature roasting is 600 ~ 1200 ℃, and the time of high-temperature roasting is 3 ~ 30h, and the atmosphere in the resistance furnace is the gaseous mixture of air or air and oxygen.

Progressive of the present invention is: raw materials used cheap and easy to get, the preparation method operates easily and controls, and the big and stable performance of products therefrom tap density is fit to suitability for industrialized production; Through the synergy of multiple transition metal ions, gained stratiform solid solution positive electrode good conductivity, specific capacity high (more than 200 mAh/g), and have good cyclical stability.

Embodiment:

Embodiment 1

Manganese dioxide 60.858 g, titanium dioxide 2.795 g, chrome green 7.6 g, lithium carbonate 43.041 g and 120mL deionized water are added in the planetary ball mill; Dry down at 110 ℃ behind the high speed ball milling 8h; Then in Muffle furnace with 900 ℃ of roasting 7h; With pulverizing after the stove cooling, just obtain 0.5Li [Li 0.33Mn 0.6Ti 0.07] O 2-0.5Li [Mn 0.8Cr 0.2] O 2Stratiform solid solution positive electrode.

The tap density of using the tap density appearance to record this positive electrode powder is 2.2 g/cm 3With the lithium sheet is that negative pole is assembled into button cell, at room temperature carries out charge-discharge test, voltage range 2.5 ~ 4.7 V, current density 30 mAh/g.The first discharge specific capacity of this material is 235 mAh/g, and circulating, capability retention is 95% after 30 times.

 

Embodiment 2

Manganese sesquioxide managnic oxide 46.417 g, titanium dioxide 3.195 g, chromium trioxide 18 g, di-iron trioxide 4.791 g, hydronium(ion) oxidation lithium 47.51 g and 150mL alcohol are added in the planetary ball mill; Dry down at 80 ℃ behind the high speed ball milling 5h; Then in Muffle furnace with 850 ℃ of roasting 10h; With pulverizing after the stove cooling, just obtain 0.4Li [Li 0.33Mn 0.57Ti 0.1] O 2-0.6Li [Mn 0.6Cr 0.3Fe 0.1] O 2Stratiform solid solution positive electrode.Test condition is with embodiment 1, and the tap density of this material is 2.1 g/cm 3, first discharge specific capacity is 220 mAh/g, circulating, capability retention is 96% after 30 times.

Embodiment 3

Manganese carbonate 56.555 g, titanium dioxide 2.396 g, chrome green 12.16 g, nickel monoxide 8.963 g, hydronium(ion) oxidation lithium 50.28 g and 180mL alcohol are added in the planetary ball mill; Dry down at 70 ℃ behind the high speed ball milling 10h; Then in continuing to be connected with the Muffle furnace of minor amounts of oxygen with 800 ℃ of roasting 12h; With pulverizing after the stove cooling, just obtain 0.6Li [Li 0.33Mn 0.62Ti 0.05] O 2-0.4Li [Mn 0.3Cr 0.4Ni 0.3] O 2Stratiform solid solution positive electrode.Test condition is with embodiment 1, and the tap density of this material is 2.0 g/cm 3, first discharge specific capacity is 241 mAh/g, circulating, capability retention is 93% after 30 times.

 

Embodiment 4

Mangano-manganic oxide 48.891 g, titanium dioxide 1.198 g, chromium trioxide 21 g, zinc oxide 2.849 g, lithium carbonate 40.603 g and 150mL alcohol are added in the planetary ball mill; Dry down at 60 ℃ behind the high speed ball milling 7h; Continuing to be connected with in the Muffle furnace of minor amounts of oxygen with 800 ℃ of roasting 10h then; With pulverizing after the stove cooling, just obtain 0.3Li [Li 0.33Mn 0.62Ti 0.05] O 2-0.7Li [Mn 0.65Cr 0.3Zn 0.05] O 2Stratiform solid solution positive electrode.Test condition is with embodiment 1, and the tap density of this material is 2.0 g/cm 3, first discharge specific capacity is 229 mAh/g.

 

Embodiment 5

Manganese dioxide 44.774 g, titanium dioxide 1.597 g, chromium trioxide 15 g, nickel sesquioxide 8.269 g, zinc oxide 4.071 g, hydronium(ion) oxidation lithium 48.895 g and 20mL deionized water, 150mL alcohol are added in the planetary ball mill; Dry down at 100 ℃ behind the high speed ball milling 12h; Then in Muffle furnace with 850 ℃ of roasting 10h; With pulverizing after the stove cooling, just obtain 0.5Li [Li 0.33Mn 0.63Ti 0.04] O 2-0.5Li [Mn 0.4Cr 0.3Ni 0.2Zn 0.1] O 2Stratiform solid solution positive electrode.Test condition is with embodiment 1, and the tap density of this material is 2.1 g/cm 3, first discharge specific capacity is 225 mAh/g.

Claims (6)

1. anode material for lithium-ion batteries, it is characterized in that: chemical formula is xLi [Li 1/3Mn 2/3-aTi a] O 2-(1-x) Li [Mn 1-b-cCr bM c] O 2, wherein, 0<x<1,0.04≤a≤0.1,0.06≤b≤0.6,0≤c≤0.3, M is one or both among Fe, Ni, the Zn, and this material has the crystal structure of stratiform.
2. the preparation method of an anode material for lithium-ion batteries; It is characterized in that: the compound of lithium, manganese, titanium, chromium, M is (1+0.33x) by the element mol ratio: [1-b-c-(0.33+a-b-c) x]: ax: b (1-x): c (1-x) weighs; Abundant ball mill mixing in being added with the ball mill of an amount of solvent medium; Gained mixture oven dry back high-temperature roasting in resistance furnace is cooled to room temperature then.
3. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 2 is characterized in that: the compound of said lithium is a kind of in lithium carbonate, the lithium hydroxide; The compound of manganese is a kind of in manganese dioxide, manganese sesquioxide managnic oxide, mangano-manganic oxide, the manganese carbonate; The compound of titanium is a titanium dioxide; The compound of chromium is a kind of in chrome green, the chromium trioxide; The compound that contains M is one or both in iron oxide, nickel oxide, the zinc oxide.
4. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 2, it is characterized in that: the time of said mechanical milling process is 1 ~ 20h, solvent medium is water, alcohol or the mixture of the two.
5. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 2, it is characterized in that: said drying course carries out under 50 ~ 120 ℃ temperature.
6. the preparation method of a kind of anode material for lithium-ion batteries as claimed in claim 2, it is characterized in that: the temperature of said high-temperature roasting is 600 ~ 1200 ℃, and the time of high-temperature roasting is 3 ~ 30h, the atmosphere in the resistance furnace is the gaseous mixture of air or air and oxygen.
CN201110275835A 2011-09-18 2011-09-18 Lithium ion battery cathode material and preparation method thereof CN102306762A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1571193A (en) * 2003-04-03 2005-01-26 索尼株式会社 Cathode material, method of manufacturing the same, and battery using the same
CN101207201A (en) * 2006-12-13 2008-06-25 三星Sdi株式会社 Cathode active material for lithium battery, cathode containing the same and lithium battery using the same
JP2011028999A (en) * 2009-07-24 2011-02-10 Kanagawa Univ Cathode material for lithium ion battery and lithium ion battery using the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1571193A (en) * 2003-04-03 2005-01-26 索尼株式会社 Cathode material, method of manufacturing the same, and battery using the same
CN101207201A (en) * 2006-12-13 2008-06-25 三星Sdi株式会社 Cathode active material for lithium battery, cathode containing the same and lithium battery using the same
JP2011028999A (en) * 2009-07-24 2011-02-10 Kanagawa Univ Cathode material for lithium ion battery and lithium ion battery using the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《电源技术》 20090531 张联齐等 Li过量的层状结构锂离子电池材料Li1+xM1-xO2(x>=0)-I. LiAO2-Li2BO3(A=Co,Ni,Cr...;B=Mn,Ti...)固熔体材料 1-6 第3卷, 第5期 *
张联齐等: "Li过量的层状结构锂离子电池材料Li1+xM1-xO2(x≥0)—I. LiAO2-Li2BO3(A=Co,Ni,Cr…;B=Mn,Ti…)固熔体材料", 《电源技术》 *

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Application publication date: 20120104