CN103000886A - Preparation method of lithium magnesium silicate composite material of lithium ion battery - Google Patents

Preparation method of lithium magnesium silicate composite material of lithium ion battery Download PDF

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Publication number
CN103000886A
CN103000886A CN2012103919095A CN201210391909A CN103000886A CN 103000886 A CN103000886 A CN 103000886A CN 2012103919095 A CN2012103919095 A CN 2012103919095A CN 201210391909 A CN201210391909 A CN 201210391909A CN 103000886 A CN103000886 A CN 103000886A
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Prior art keywords
lithium
solution
sintering
ion battery
composite material
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CN2012103919095A
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Chinese (zh)
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姜波
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SHANGHAI JINZHONG INFORMATION TECHNOLOGY Co Ltd
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SHANGHAI JINZHONG INFORMATION TECHNOLOGY Co Ltd
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Priority to CN2012103919095A priority Critical patent/CN103000886A/en
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a preparation method of a lithium magnesium silicate composite material of a lithium ion battery. The preparation method comprises the following steps: (1) weighing lithium oxalate, manganous nitrate and tetraethyl orthosilicate according to a chemical formula Li2MnSiO4; (2) dissolving the lithium oxalate, the manganous nitrate and cane sugar in distilled water at room temperature to form a solution A, dissolving tetraethyl orthosilicate and acetic acid in distilled water, and stirring to form a solution B, adding the solution A into the solution B, stirring under the protection of inert gas to form sol gel; (3) carrying out water washing, filtering and drying on the sol gel, and then carrying out mechanical ball milling on a product to obtain precursor powder; and (4) sintering three times to obtain the lithium magnesium silicate composite material with complete carbon coating. The anode material of the lithium ion battery, prepared according to the invention, is uniform and delicate, is high in density and large in specific surface, is completely coated with carbon so as to achieve the high specific capacity and good electric conductivity at the same time, and is high in specific capacity, good in cyclic stability and long in service life when applied to the lithium ion battery.

Description

A kind of preparation method of lithium ion battery silicic acid manganese lithium composite material
Technical field
The present invention relates to a kind of lithium ion battery material preparation method, relate in particular to a kind of preparation method of lithium ion battery silicic acid manganese lithium composite material, lithium ion battery silicic acid manganese lithium composite material and a kind of lithium ion electronics prepared by described method.
Background technology
Lithium ion battery, as a kind of novel secondary cell, has the advantages that specific capacity is high, voltage is high, fail safe is good, is widely used in the driving power of electric automobile, mobile phone, notebook computer.
Positive electrode, as one of core of lithium ion battery, is the key link of restriction lithium ion battery development, is also the focus of always people's research.Positive electrode is one of key factor affected lithium ion battery.Current commercial lithium ion cell positive material mainly contains LiCoO 2, LiFePO 4, Li 2mnO 4and the ternary system material, yet these materials have problems separately: LiCoO 2synthetic easily, charge-discharge performance is stable, but metallic cobalt is expensive, and Charging state LiCoO 2poor heat stability, fail safe is not good enough, can not meet the needs of the motive-power batteries such as electric vehicle power sources; Li 2mnO 4with low cost, but due to Mn 3+dissolving and Jahn-Teller effect make this material cycle performance bad, security performance is also bad; LiFePO 4the good cycle of material, but electronic conductivity and tap density are difficult to improve simultaneously.
Therefore, high, the Heat stability is good of exploitation specific capacity, positive electrode cheap, that fail safe is good are the keys of further widening the application of lithium ion battery and realizing sustainable development.Silicate-based material is a kind of new electrode materials that development in recent years is got up, the characteristics such as it has that with low cost, environmental protection, security performance are good, Stability Analysis of Structures, chemical property are better, be subject to the researcher and paid attention to widely, become one of the most potential anode material for lithium-ion batteries.As with LiFePO 4be both the Li of polyanion type positive electrode 2mnSiO 4, due to the Mn aboundresources, have two can freely take off the lithium ion of embedding and there is larger theoretical specific capacity, and there is higher fail safe and environment friendly and receive people's concern.Current Li 2mnSiO 4the preparation method, the material granule obtained is large, and density is low, and specific area is little, and the electronic conductivity chemical property does not obviously improve.Therefore need a kind of preparation method to obtain the manganese silicate of lithium composite material that specific area is large, density is large, electronic conductivity is high.
Summary of the invention
The preparation method who the objective of the invention is a kind of lithium ion battery silicic acid manganese lithium composite material, the lithium ion battery of the lithium ion manganese silicate of lithium composite material that uses the method to prepare has the characteristics such as height ratio capacity, excellent cycling stability, long service life.
To achieve these goals, the preparation method of a kind of lithium ion battery silicic acid manganese lithium composite material provided by the invention comprises the steps:
Step 1, batching
According to chemical formula Li 2mnSiO 4, the ratio that is 2: 1: 1 according to Li element, Mn element and Si element mol ratio takes respectively lithium oxalate, manganese nitrate and tetraethoxysilane;
Step 2, liquid phase reactor
Above-mentioned lithium oxalate, manganese nitrate and sucrose at room temperature are dissolved in distilled water, form solution A, wherein the mol ratio of sucrose and lithium oxalate is 1: 0.1-0.5, and in solution A, the concentration of lithium salts is 1-3mol/L;
By tetraethoxysilane and acetic acid according to 1: the mol ratio of 6-8 is dissolved in distilled water, then under 70 ℃, inert gas shielding, carry out magnetic agitation 10-20 minute with the rotating speed of 100-200 rev/min, form solution B, in solution B, the concentration of tetraethoxysilane is 0.1-1mol/L;
According to solution A and solution B, be 1: the volume ratio of 1-2 is by solution A to entering in solution B, and under inert gas shielding, under the temperature condition that is 80-100 ℃, the rotating speed of 100-200 rev/min carries out magnetic agitation 2-4 hour, forms colloidal sol;
Step 3, drying makes precursor powder
Step 4, sintering
First sintering: join concentration in precursor powder and be more than or equal in 85% alcohol dispersant, and ground 1-2 hour in grinder, continue to grind 2-4 hour after adding the Graphene that accounts for presoma weight 20-30%, then under 110-130 ℃ of oxygen free condition, carry out drying;
Sintering for the second time: the material made after dry is carried out to sintering for the second time, and the Temperature Setting of sintering is at 300-350 ℃;
Sintering for the third time: the material made after sintering for the second time carries out sintering for the third time, and the Temperature Setting of sintering, at 800-950 ℃, obtains carbon and coats complete manganese silicate of lithium composite material.
Wherein, step 3 method of operation is preferably: by described colloidal sol through washing 3-4 time, filter, after 60-80 ℃ of lower vacuumize 12-24h, then the mechanical ball milling of product, after 1-3 hour, is obtained to precursor powder.
Second purpose of the present invention is to provide a kind of as prepared by above-mentioned any means lithium ion battery silicic acid manganese lithium composite material.
The 3rd purpose of the present invention is to provide a kind of lithium ion battery that contains manganese silicate of lithium composite material prepared by above-mentioned any means.
Anode material for lithium-ion batteries prepared by the present invention, uniform and smooth, density is high, and specific surface is large, and the complete carbon that coated, therefore, when thering is height ratio capacity, also there is good conductivity, during for lithium ion battery, specific capacity is high, good cycling stability, long service life.
Embodiment
embodiment mono-
batching
According to chemical formula Li 2mnSiO 4, the ratio that is 2: 1: 1 according to Li element, Mn element and Si element mol ratio takes respectively lithium oxalate, manganese nitrate and tetraethoxysilane.
liquid phase reactor
Above-mentioned lithium oxalate, manganese nitrate and sucrose at room temperature are dissolved in distilled water, form solution A, wherein the mol ratio of sucrose and lithium oxalate is 1: 0.1, and in solution A, the concentration of lithium salts is 1mol/L.Put into reactor after being dissolved in distilled water by tetraethoxysilane and acetic acid according to the mol ratio of 1: 6; then under 70 ℃, inert gas shielding; carry out magnetic agitation 10 minutes with the rotating speeds of 100 rev/mins, form solution B, in solution B, the concentration of tetraethoxysilane is 0.1mol/L.The volume ratio that is 1: 1 according to solution A and solution B is by solution A to entering in solution B, and under inert gas shielding, under the temperature condition that is 80 ℃, the rotating speed of 100 rev/mins carries out magnetic agitation 2 hours, forms colloidal sol.
drying makes precursor powder
By described colloidal sol through wash 3 times, filter, after 60 ℃ of lower vacuumize 12h, then product machinery ball milling, after 1 hour, is obtained to precursor powder.
sintering
First sintering: join concentration in precursor powder and be more than or equal in 85% alcohol dispersant, and in grinder, ground 1 hour, continue to grind 2 hours after adding the Graphene that accounts for presoma weight 20%, then under 110 ℃ of oxygen free conditions, carry out drying; Sintering for the second time: the material made after dry is carried out to sintering for the second time, and the Temperature Setting of sintering is at 300 ℃; Sintering for the third time: the material made after sintering for the second time carries out sintering for the third time, and the Temperature Setting of sintering, at 800 ℃, obtains carbon and coats complete manganese silicate of lithium composite material.
embodiment bis-
batching
According to chemical formula Li 2mnSiO 4, the ratio that is 2: 1: 1 according to Li element, Mn element and Si element mol ratio takes respectively lithium oxalate, manganese nitrate and tetraethoxysilane.
liquid phase reactor
Above-mentioned lithium oxalate, manganese nitrate and sucrose at room temperature are dissolved in distilled water, form solution A, wherein the mol ratio of sucrose and lithium oxalate is 1: 0.5, and in solution A, the concentration of lithium salts is 3mol/L.Put into reactor after being dissolved in distilled water by tetraethoxysilane and acetic acid according to the mol ratio of 1: 8; then under 70 ℃, inert gas shielding; carry out magnetic agitation 20 minutes with the rotating speeds of 200 rev/mins, form solution B, in solution B, the concentration of tetraethoxysilane is 1mol/L.The volume ratio that is 1: 2 according to solution A and solution B is by solution A to entering in solution B, and under inert gas shielding, under the temperature condition that is 100 ℃, the rotating speed of 200 rev/mins carries out magnetic agitation 4 hours, forms colloidal sol.
drying makes precursor powder
By described colloidal sol through wash 4 times, filter, after 80 ℃ of lower vacuumize 24h, then product machinery ball milling, after 3 hours, is obtained to precursor powder.
sintering
First sintering: join concentration in precursor powder and be more than or equal in 85% alcohol dispersant, and in grinder, ground 2 hours, continue to grind 4 hours after adding the Graphene that accounts for presoma weight 30%, then under 130 ℃ of oxygen free conditions, carry out drying; Sintering for the second time: the material made after dry is carried out to sintering for the second time, and the Temperature Setting of sintering is at 350 ℃; Sintering for the third time: the material made after sintering for the second time carries out sintering for the third time, and the Temperature Setting of sintering, at 950 ℃, obtains carbon and coats complete manganese silicate of lithium composite material.
comparative example
Get 9ml ethanol and 1ml water is mixed with mixed solution, add the 5.200g teos solution, stir; The MnCl that adds 4.950g 2 .4H 2o, stir; The LiOH of 2.100g is added in the solution of above-mentioned steps preparation, stir; With acetic acid and ethylenediamine, the pH value is adjusted to 10, the solution finally prepared is inserted in reactor, 220 ℃ of lower solvent thermal reactions 48 hours, and water cyclic washing 5 times, the alcohol washed twice, filter, and is drying to obtain the manganese silicate of lithium material under 105 ℃.
By embodiment mono-, two and comparative example gained manganese silicate of lithium material, make electrode slice respectively, be assembled into battery.Polypropylene screen (Celgard 3501) is as barrier film, and the lithium metal is as negative pole, 1M LiPF 6be dissolved in the ethyl carbonate of 1: 1 volume mixture and dimethyl carbonate as electrolyte.Being evaluated on Arbin cell tester BT-2000 (Arbin Instruments, College Station, TX) of chemical property carried out.At room temperature, the test of half-cell high rate performance is carried out in 3 to 4.3V voltage ranges.After tested this embodiment mono-with two material with the material of comparative example, compare, more than first discharge specific capacity has promoted 40-50%, cycle life has improved 2-3 doubly.

Claims (4)

1. the preparation method of a lithium ion battery silicic acid manganese lithium composite material, is characterized in that, comprises the steps:
Step 1, batching
According to chemical formula Li 2mnSiO 4, the ratio that is 2: 1: 1 according to Li element, Mn element and Si element mol ratio takes respectively lithium oxalate, manganese nitrate and tetraethoxysilane;
Step 2, liquid phase reactor
Above-mentioned lithium oxalate, manganese nitrate and sucrose at room temperature are dissolved in distilled water, form solution A, wherein the mol ratio of sucrose and lithium oxalate is 1: 0.1-0.5, and in solution A, the concentration of lithium salts is 1-3mol/L;
By tetraethoxysilane and acetic acid according to 1: the mol ratio of 6-8 is dissolved in distilled water, then under 70 ℃, inert gas shielding, carry out magnetic agitation 10-20 minute with the rotating speed of 100-200 rev/min, form solution B, in solution B, the concentration of tetraethoxysilane is 0.1-1mol/L;
According to solution A and solution B, be 1: the volume ratio of 1-2 is by solution A to entering in solution B, and under inert gas shielding, under the temperature condition that is 80-100 ℃, the rotating speed of 100-200 rev/min carries out magnetic agitation 2-4 hour, forms colloidal sol;
Step 3, drying makes precursor powder
Step 4, sintering
First sintering: join concentration in precursor powder and be more than or equal in 85% alcohol dispersant, and ground 1-2 hour in grinder, continue to grind 2-4 hour after adding the Graphene that accounts for presoma weight 20-30%, then under 110-130 ℃ of oxygen free condition, carry out drying;
Sintering for the second time: the material made after dry is carried out to sintering for the second time, and the Temperature Setting of sintering is at 300-350 ℃;
Sintering for the third time: the material made after sintering for the second time carries out sintering for the third time, and the Temperature Setting of sintering, at 800-950 ℃, obtains carbon and coats complete manganese silicate of lithium composite material.
2. method according to claim 1, is characterized in that, step 3 method of operation is: by described colloidal sol through washing 3-4 time, filter, after 60-80 ℃ of lower vacuumize 12-24h, then the mechanical ball milling of product, after 1-3 hour, is obtained to precursor powder.
3. the lithium ion battery silicic acid manganese lithium composite material that as claimed in claim 1 prepared by method.
4. a lithium ion battery that contains the described manganese silicate of lithium composite material of claim 3.
CN2012103919095A 2012-10-16 2012-10-16 Preparation method of lithium magnesium silicate composite material of lithium ion battery Pending CN103000886A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236432A (en) * 2015-09-07 2016-01-13 东莞市迈科科技有限公司 Preparation method of manganese lithium silicate cathode material
CN105576205A (en) * 2015-12-21 2016-05-11 宁波高新区锦众信息科技有限公司 Method for preparing carbon-coated silicic acid, manganese and lithium composite materials for lithium ion batteries
CN105977486A (en) * 2016-06-22 2016-09-28 浙江大学 Preparation method and application of sodium-rich transition metal silicate as sodium ion battery cathode material
CN106229512A (en) * 2016-08-12 2016-12-14 中南大学 A kind of battery preparation method of 3-D ordered multiporous silicate/C composite

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236432A (en) * 2015-09-07 2016-01-13 东莞市迈科科技有限公司 Preparation method of manganese lithium silicate cathode material
CN105576205A (en) * 2015-12-21 2016-05-11 宁波高新区锦众信息科技有限公司 Method for preparing carbon-coated silicic acid, manganese and lithium composite materials for lithium ion batteries
CN105977486A (en) * 2016-06-22 2016-09-28 浙江大学 Preparation method and application of sodium-rich transition metal silicate as sodium ion battery cathode material
CN105977486B (en) * 2016-06-22 2018-09-11 浙江大学 A kind of preparation method and application of the rich sodium transition metal silicate as sodium-ion battery positive material
CN106229512A (en) * 2016-08-12 2016-12-14 中南大学 A kind of battery preparation method of 3-D ordered multiporous silicate/C composite

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Application publication date: 20130327