CN1482068A - Wet chemical synthesis of positive electrode material of Li-ion battery - Google Patents

Wet chemical synthesis of positive electrode material of Li-ion battery Download PDF

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CN1482068A
CN1482068A CNA021143919A CN02114391A CN1482068A CN 1482068 A CN1482068 A CN 1482068A CN A021143919 A CNA021143919 A CN A021143919A CN 02114391 A CN02114391 A CN 02114391A CN 1482068 A CN1482068 A CN 1482068A
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lithium
compound
spinel
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CN1203003C (en
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李运姣
李洪桂
赵中伟
孙培梅
霍广生
孙召明
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Central South University
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Abstract

The wet chemical synthesis of lithium ion cell positive electrode material belongs to the field of functional material and wet chemical process. Manganese compound is added into water solution of lithium-containing compound, and through the chemical reaction between manganese compound and lithium compound spinel type Li-Mn compound crystal is synthesized directly in one step. The present invention completes the homogeneous mixing of Li, Mn, O and doping element in atomic level, and the Li embedding amount in the product may be controlled precisely via the concentration and amount of Li compound and other technological parameters. The product has homogeneous chemical components and physical phase components, easy-to-control granularity and appearance and excellent electrochemical performance. The present invention has low cost, simple process and simple operation, and is easy to use in industrial production.

Description

A kind of wet chemical synthesis of anode material for lithium-ion batteries
[technical field] the present invention relates to a kind of wet chemical synthesis of lithium battery anode material lithium Mn oxide.
[background technology] spinel lithium-manganese oxide is because of aboundresources, low price, and environmental friendliness is acknowledged as the anode active material of lithium ion battery that development potentiality is arranged most.At present, spinel lithium-manganese oxide (LiMn 2O 4) synthetic method mainly contain solid-phase synthesis and wet-chemical synthesis method two big classes.Solid-phase synthesis be people study also be the earliest study the most sophisticated a kind of method, but owing to temperature of reaction height, long reaction time cause the volatilization loss of energy consumption height and lithium serious, the restriction of solid state reaction itself in addition, be difficult to realize the uniform mixing of molecular level level, the homogeneity of products therefrom is bad, and chemical property is relatively poor.And wet chemistry method carries out in solution system owing to the preparation of product or presoma, can realize the mixing of molecule or atom level level, have product component and even particle size distribution, pattern and microtexture and outstanding advantage such as can artificially control, caused people's great attention.Most representative wet chemical synthesis has sol-gel method, Pechini method, coprecipitation method etc.These wet chemical methods all comprise liquid-phase mixing-evaporation-high-temperature heat treatment three big steps, and lithium salts molecule and manganese salt only take place its liquid-phase mixing process, and [most of situation is the hydrolysate Mn (OH) of bivalent manganese 2] physical mixed, behind the heating evaporation, the lithium salts molecule is by the surface of physical adsorption at manganic compound, the oxidation of bivalent manganese and need finish at high-temperature heat treatment process with the reaction bonded of lithium ion.This causes flow process tediously long on the one hand, fails to realize the uniform mixing of atom or ion level level on the other hand, i.e. the rearrangement of the formation reaction of lithium manganese oxide and structure still need at high temperature be carried out.In addition, sol-gel method and the used organic reagent of Pechini method often cost an arm and a leg, and cause preparation cost to increase.
Liu Xingquan etc. disclose a kind of with MnO in " synthetic chemistry " the 7th volume the 4th phase (1999) P382-388 2And LiOHH 2O is a raw material, carries out the method for the synthetic lithium manganese oxide of hydro-thermal reaction of 72h in autoclave under 240 ℃, and the product that obtains is a multiphase mixture, except that contain the spinel thing mutually, also contain the Li of rock salt laminate structure 2MnO 3And γ-Mn 2O 3Etc. multiple dephasign, and its XRD figure spectrum Tipping Center spathous characteristic peak is not obvious.In the XRD figure of this hydro-thermal synthetic product behind 650 ℃ of following thermal treatment 6h, still there is more α-Mn 2O 3, KMn 8O 16And γ-MnO 2Deng dephasign, so do not obtain the spinel lithium-manganese oxide of single phase structure.People such as Liu Xingquan disclose a kind of method that adopts in-situ oxidation precipitate reduction hydrothermal synthesis method to prepare spinel lithium-manganese oxide in " SCI " the 23rd volume the 2nd phase (2002) P179-181, this method is with Mn (NO 3) 26H 2O and Mn (CH 3COO) 24H 2O is the manganese source, with LiOHH 2O is lithium source and precipitation agent, uses H 2O 2Make oxygenant, earlier redox precipitation is taken place in manganese source, lithium source, precipitation agent and oxygenant etc. under normal pressure, and then the gained slip changed over to the hydrothermal crystallizing that under 200～260 ℃, carries out 6～72h in the autoclave, product behind the filtration washing is dry 12h under 105 ℃, gets end product through high-temperature heat treatment more at last---spinel lithium-manganese oxide.The formation of its spinel lithium-manganese oxide is finished in two kinds of distinct devices respectively by atmospheric pressure oxidation precipitate reduction and two steps of hydrothermal crystallizing, and flow process is longer, and the atmospheric pressure oxidation reduction process need add special oxygenant H 2O 2, because H 2O 2Very easily decompose, the bad control of the oxidation state of its utilization ratio and manganese, and then make the composition (particularly lithium content) of product be difficult to adjust flexibly and accurately control.
[summary of the invention] is in order to solve above deficiency, the invention provides a kind of in the aqueous solution method of the spinel lithium manganese oxide by the chemical reaction one-step synthesis crystal form between manganic compound and the lithium compound, with chemical ingredients and the thing phase composition of controlling lithium manganese oxide effectively, improve the homogeneity of its granularity, pattern and structure, improve its chemical property; Simplify synthesis technique simultaneously, reduce preparation cost.
The present invention adds manganic compound in the aqueous solution of lithium-containing compound, under 80～250 ℃, by direct synthesizing crystalline spinel lithium manganese oxide of one step of the chemical reaction between manganic compound and the lithium compound.During the preparation doped lithium manganese oxide, add the compound of doped element M, doped element M comprises Cr, Co, Ni, V.
Main processes of the present invention and parameter are as follows:
1. the wet-chemical reaction is synthetic
The aqueous solution of manganic compound and lithium compound is added in the reactor, the lithium compound consumption is 1.0～4.0 times of theoretical amount, temperature of reaction is 80～250 ℃, pressure is 0.1～3.9Mpa, the insulation reaction time is 2～48h, behind the gained slurry filtration with deionized water or ethanol or methanol wash, then at 105～110 ℃ of following oven dry 4～12h, make chemical ingredients and thing phase composition evenly, the Li/Mn mol ratio is between 0.40～1.0 spinel lithium-manganese oxide.
Described manganic compound comprises two or more the mixture at least in Manganse Dioxide, manganic oxide, trimanganese tetroxide, manganese monoxide, manganous hydroxide, hydroxyl oxidize manganese, manganous sulfate, manganous nitrate, Manganous chloride tetrahydrate, manganous acetate, potassium permanganate, potassium manganate, the high manganese lithium; Described lithium compound comprises at least a or multiple mixture in Quilonum Retard, lithium chloride, lithium hydroxide, lithium acetate, lithium nitrate, the Lithium Sulphate.
During the preparation doped lithium manganese oxide, then add the compound of doped element M simultaneously, the compound of M can be CoCl 2, CoSO 4, CrCl 3, K 2Cr 2O 7
2. high-temperature heat treatment
With the wet-chemical synthetic product in air atmosphere in 300～850 ℃ of following thermal treatment 2～24h, obtain the more complete spinel Li of crystalline structure xM yMn 2-yO 4
Chemical constitution according to the aforesaid method products obtained therefrom is Li xM yMn 2-yO 4, wherein: 0＜x≤2,0≤y≤1, Li/Mn (mol than) is 0.4～1.0, doped element M is one or more the mixture among Cr, Co, Ni, the V, and:
Work as x=1, during y=0, product is stoichiometry spinel LiMn 2O 4
When 0＜x＜1 and 1＜x≤2, during y=0, product is nonstoichiometry spinel Li xMn 2O 4
When 0＜x≤2,0＜y≤1 o'clock, product is doped spinel Li xM yMn 2-yO 4
The present invention goes on foot the spinel Li of direct synthesizing crystalline by the chemical reaction between manganic compound and the lithium compound one in the aqueous solution xM yMn 2-yO 4Positive electrode active materials;
1. building-up process is finished by one step of chemical reaction in the aqueous solution, realized Li, Mn, O and doped element uniform mixing in the atom level level, thereby the lithium-inserting amount of products therefrom can accurately be controlled by the adjustment of processing parameters such as lithium compound concentration and consumption, and chemical ingredients and thing phase composition are even, granularity and pattern are easy to control, and chemical property is good;
2. raw materials used is MnO 2Reach common mineral compound such as LiOH, its wide material sources, low price, and need not add special oxygenant, therefore, synthetic cost is low;
3. Li xM yMn 2-yO 4Building-up reactions and the rearrangement of structure and three processes of crystallization step in a kind of equipment finish, and belong to general wet-chemical process, thereby flow process is simple, easy and simple to handle, be easy to realize industrialization.
[description of drawings]
Fig. 1: principle process flow sheet of the present invention.
Fig. 2: gained nonstoichiometry spinel Li of the present invention 1.04Mn 1.96O 4XRD analysis collection of illustrative plates before the thermal treatment.
Fig. 3: gained nonstoichiometry spinel Li of the present invention 1.04Mn 1.96O 4XRD analysis collection of illustrative plates after the thermal treatment.
Fig. 4: gained Co-doped spinel Li of the present invention 1.02Co 0.04Mn 1.94O 4XRD analysis collection of illustrative plates before the thermal treatment.
Fig. 5: gained Co-doped spinel Li of the present invention 1.02Co 0.04Mn 1.94O 4XRD analysis collection of illustrative plates after the thermal treatment.
Fig. 6: gained of the present invention is mixed picotite Li 1.04Cr 0.03Mn 1.93O 4XRD analysis collection of illustrative plates before the thermal treatment.
Fig. 7: gained of the present invention is mixed picotite Li 1.04Cr 0.03Mn 1.93O 4XRD analysis collection of illustrative plates after the thermal treatment.
Fig. 8: SEM pattern after the gained lithium manganese oxide of the present invention thermal treatment (80 ℃ of synthetic 48h of wet-chemical, 800 ℃ of thermal treatment 24h).
Fig. 9: SEM pattern after the gained lithium manganese oxide of the present invention thermal treatment (200 ℃ of synthetic 12h of wet-chemical, 700 ℃ of thermal treatment 8h).
[embodiment]
1. with MnO 2With Mn 2O 3And MnSO 4Mixture 30g (by theoretical proportioning) and LiOH solution 600ml (the Li consumption is 1.05 times of theoretical amount) add in the reactor, in 250 ℃ of reaction 12h down, filter and with behind the deionized water wash in 105 ℃ of oven dry 12h down.Gained wet-chemical synthetic product contains Li4.03%, Mn60.25%, and Li/Mn (mol ratio) is 0.53, chemical formula is Li 1.04Mn 1.96O 4It has cubic spinel structure [Fig. 2] the X-ray diffraction analytical proof, but contains a small amount of Mn 3O 4In 850 ℃ of following air atmospheres behind the thermal treatment 2h, Mn 3O 4Disappear mutually, change that crystalline structure is more complete, the rich lithium-spinel product [Fig. 3] of phase composition homogeneous into.It is at 1.0M LiClO 4(1: 1wt) in the electrolytic solution, carry out charge-discharge performance test under 0.2C and 3.5～4.35V condition, the initial charge capacity is 126.3mAh/g to/EC+DEC, and loading capacity is 118.4mAh/g first, circulates after 20 times, and loading capacity is 116.0mAh/g.
2. with MnO 2With Mn (OH) 2And Mn 3O 4Mixture 50g (by theoretical proportioning) and LiCl and the mixing solutions 500ml (the Li consumption is 1.05 times of theoretical amount) of LiOH add in the reactor, add doping element compound CoCl simultaneously 2Solution 10ml, in 220 ℃ of following reaction 8h, filter and with after the washing with alcohol in 105 ℃ of oven dry 8h down.Products therefrom contains Li3.96%, Mn59.12%, and Co1.32%, Li/Mn (mol ratio) is 0.53, chemical formula is Li 1.03Co 0.04Mn 1.93O 4X-ray diffraction analysis proves that it has cubic spinel structure [Fig. 4], but contains a small amount of Mn 3O 4Dephasign.In 750 ℃ of following air atmospheres, be transformed into single spinel structure [Fig. 5] behind the thermal treatment 2h.It is at 1.0M LiClO 4(1: 1wt) in the electrolytic solution, carry out charge-discharge performance test under 0.2C and 3.5～4.35V condition, the initial charge capacity is 128.5mAh/g to/EC+DEC, and loading capacity is 119.7mAh/g first, circulates after 20 times, and loading capacity is 116.6mAh/g.
3. with Mn (CH 3COO) 2With Mn 3O 4And KMnO 4Mixture 40g (by theoretical proportioning) and CH 3The mixing solutions 600ml of COOLi and LiOH (the Li consumption is 1.05 times of theoretical amount) adds in the reactor, adds doping element compound CrCl simultaneously 3.0g, in 230 ℃ of following reaction 8h, filter and with behind the deionized water wash in 110 ℃ of oven dry 12h, products therefrom contains Li3.97%, Mn59.23%, Cr1.09%, K0.0012%, Li/Mn (mol than) is 0.53, chemical formula is Li 1.03Cr 0.04Mn 1.93O 4X-ray diffraction analysis proves that it has single cubic spinel structure [Fig. 6].This wet-chemical synthetic product crystalline structure become more complete [Fig. 7] behind the thermal treatment 8h in 700 ℃ of following air atmospheres.
4. with Mn (OH) 2With Mn 3O 4And KMnO 3Mixture 70g (by theoretical proportioning), KVO 32g and LiOH and LiNO 3Mixing solutions 600ml (the Li consumption is 1.5 times of theoretical amount) add together in the reactor, in 220 ℃ of reaction 2h, filter and with after the methanol wash in 105 ℃ of oven dry 8h.Products therefrom contains Li3.85%, Mn59.47%, and V1.22%, Li/Mn (mol ratio) is: 0.51, chemical formula is LiV 0.04Mn 1.96O 4, X-ray diffraction analysis proves that it has the cubic spinel structure, and behind the thermal treatment 12h, its characteristic peak becomes more sharp-pointed in 500 ℃ of following air atmospheres, and it is more complete that crystalline structure is tending towards.
5.Mn 3O 4With MnO 2Mixture 40g (by theoretical proportioning), NiSO 4Solution 20ml, LiOH and Li 2CO 3Mixing solutions 500ml (the Li consumption is 1.02 times of theoretical amount) add together in the reactor, 220 ℃ of following reaction 24h, filter and with after the washing with alcohol in 105 ℃ of oven dry 6h.Products therefrom contains Li3.85%, Mn60.10%, and Ni0.98%, Li/Mn (mol ratio) is 0.51, chemical formula is Li 1.0Ni 0.03Mn 1.97O 4Prove that through X-ray diffraction analysis it has the cubic spinel structure, but contain Mn 3O 4Dephasign, in 300 ℃ of following air atmospheres behind the thermal treatment 24h, Mn 3O 4Dephasign disappears, and changes single cubic spinel product into.
6.Mn (OH) 2With MnOOH and LiMnO 4Mixture 30g (by theoretical proportioning) and CH 3The mixing solutions 400ml of COOLi and LiOH (the Li consumption is 4.0 times of theoretical amount) adds in the reactor, reacts 48h down in 80 ℃.Filter and with behind the deionized water wash in 105 ℃ of oven dry 4h, thermal treatment 12h in 800 ℃ of following air atmospheres again, products therefrom contains Li3.83%, Mn60.67%, Li/Mn (mol than) is 0.50, chemical formula is LiMn 2O 4, X-ray diffraction analysis proves that it has the cubic spinel structure.
7.MnO 2With Mn (NO 3) mixed serum 300ml (by theoretical proportioning), LiOH and the LiNO of 2 (50%wt solution) 3Mixing solutions 400ml (the Li consumption is 4.0 times of theoretical amount) add together in the reactor, 220 ℃ of following reaction 12h, filter and with after the washing with alcohol in 110 ℃ of oven dry 6h, thermal treatment 12h in 700 ℃ of following air atmospheres again.Products therefrom contains Li5.60%, Mn55.58%, and Li/Mn (mol ratio) is 0.80, chemical formula is Li 1.33Mn 1.67O 4(be Li 4Mn 5O 12).Prove that through X-ray diffraction analysis it has single cubic spinel product.
8. with MnSO 4With Mn 3O 4And MnO 2Mixture 30g (by theoretical proportioning) and Li 2SO 4Add in the reactor with the mixing solutions 500ml (the Li consumption is 3.0 times of theoretical amount) of LiOH, add doping element compound K simultaneously 2Cr 2O 7Solution 150.0ml, react 8h down in 200 ℃, filter and with behind the deionized water wash in 110 ℃ of oven dry 5h, thermal treatment 12h in 500 ℃ of following air atmospheres must mix the chromium lithium manganese oxide again, and its chemical ingredients is: Li4.12%, Mn3.81%, Cr15.88%, Li/Mn (mol ratio) is 0.74, chemical formula is Li 1.05Cr 0.54Mn 1.41O 4X-ray diffraction analysis proves that it has the cubic spinel structure.

Claims (5)

1. the wet chemical synthesis of an anode material for lithium-ion batteries, it is characterized in that: the present invention adds manganic compound in the aqueous solution of lithium-containing compound, by direct synthesizing crystalline spinel lithium manganese oxide of one step of the chemical reaction between manganic compound and the lithium compound;
Main processes and parameter are as follows:
A. the wet-chemical reaction is synthetic
The aqueous solution of manganic compound and lithium compound is added in the reactor, the lithium compound consumption is 1.0～4.0 times of theoretical amount, temperature of reaction is 80～250 ℃, pressure is 0.1～3.9Mpa, the insulation reaction time is 2～48h, behind the gained slurry filtration with deionized water or ethanol or methanol wash, then at 105～110 ℃ of following oven dry 4～12h, make chemical ingredients and thing phase composition evenly, the Li/Mn mol ratio is between 0.40～1.0 spinel lithium-manganese oxide;
B. high-temperature heat treatment
With the wet-chemical synthetic product in air atmosphere in 300～850 ℃ of following thermal treatment 2～24h, obtain the more complete spinel lithium-manganese oxide of crystalline structure.
2. method according to claim 1 is characterized in that: described manganic compound comprises two or more the mixture at least in Manganse Dioxide, manganic oxide, trimanganese tetroxide, manganese monoxide, manganous hydroxide, hydroxyl oxidize manganese, manganous sulfate, manganous nitrate, Manganous chloride tetrahydrate, manganous acetate, potassium permanganate, potassium manganate, the high manganese lithium.
3. method according to claim 1 is characterized in that: described lithium compound comprises at least a or multiple mixture in Quilonum Retard, lithium chloride, lithium hydroxide, lithium acetate, lithium nitrate, the Lithium Sulphate.
4. method according to claim 1 is characterized in that: during the preparation doped lithium manganese oxide, add the compound of doped element M, doped element M comprises Cr, Co, Ni, V.
5. according to claim 1 or 2 or 3 or 4 described methods, it is characterized in that: the chemical constitution of products obtained therefrom is Li xM yMn 2-yO 4, wherein: 0＜x≤2,0≤y≤1, Li/Mn (mol than) is 0.4～1.0, doped element M is one or more the mixture among Cr, Co, Ni, the V, and:
Work as x=1, during y=0, product is stoichiometry spinel LiMn 2O 4
When 0＜x＜1 and 1＜x≤2, during y=0, product is nonstoichiometry spinel Li xMn 2O 4
When 0＜x≤2,0＜y≤1 o'clock, product is doped spinel Li xM yMn 2-yO 4
CNB021143919A 2002-09-10 2002-09-10 Wet chemical synthesis of positive electrode material of Li-ion battery Expired - Fee Related CN1203003C (en)

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EP1630891A1 (en) * 2004-08-30 2006-03-01 Shin-Kobe Electric Machinery Co., Ltd. Positive electrode active material, non-aqueous electrolyte secondary battery and method for manufacturing positive electrode active material
CN1330579C (en) * 2005-04-12 2007-08-08 武汉理工大学 Preparation of spinel type Li-Mn-oxide lithium ion screening materials by hydrothermal method
CN100371256C (en) * 2006-01-26 2008-02-27 合肥工业大学 Synthesis of series nanometer lithium and manganese oxide for lithium ion battery
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CN109742380A (en) * 2019-01-31 2019-05-10 王东升 A kind of preparation method of lithium-rich manganese-based anode material
CN115974161A (en) * 2022-03-28 2023-04-18 贵州大龙汇成新材料有限公司 Manganous manganic oxide pre-intercalated lithium intermediate and preparation method and application thereof
WO2023184656A1 (en) * 2022-03-28 2023-10-05 贵州大龙汇成新材料有限公司 Trimanganese tetraoxide lithium pre-embedded intermediate, preparation method therefor and use thereof

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