CN102290575A - Lithium ion cell anode material and preparation method thereof - Google Patents

Lithium ion cell anode material and preparation method thereof Download PDF

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CN102290575A
CN102290575A CN2011102047935A CN201110204793A CN102290575A CN 102290575 A CN102290575 A CN 102290575A CN 2011102047935 A CN2011102047935 A CN 2011102047935A CN 201110204793 A CN201110204793 A CN 201110204793A CN 102290575 A CN102290575 A CN 102290575A
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lithium
source
preparation
anode material
ion batteries
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时喜喜
刘兴江
任丽彬
孙文彬
卢志威
彭庆文
任慧琪
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CETC 18 Research Institute
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Abstract

The invention relates to a lithium ion cell anode material and a preparation method thereof. The material disclosed by the invention is Li3 plus xV2(PO4)3 minus x(SiO4)x, wherein x is larger than or equal to 0 and less than or equal to 3. The preparation method disclosed by the invention includes the following steps: (1) weighing raw materials; (2) preparing gelatinous mixture; (3) preparing precursor; (4) preparing paste; (5) preparing the Li3 plus xV2(PO4)3 minus x(SiO4)x material. Because the invention partially substitutes PO43 minus in lithium vanadium phosphate with SiO44 minus ions, the theoretical specific capacity is high, the material structure is stable, the safety performance is high, moreover, the material is easier to synthesize, the composition range of the material is broadened, and the material can be regulated into a series of products according to need.

Description

A kind of anode material for lithium-ion batteries and preparation method thereof
Technical field
The invention belongs to the battery material technical field, especially relate to a kind of anode material for lithium-ion batteries and preparation method thereof.
Background technology
Goodenough reported first in 1997 have an olivine structural LiFePO4 can reversibly embed and the removal lithium embedded ion, because the structural stability and the extraordinary security performance of phosphate excellence, be fit to very much the particularly application of electrokinetic cell of lithium ion battery, be considered to the desirable positive electrode of lithium ion battery.And in recent years, another kind of phosphate-based polyanionic positive electrode-phosphoric acid vanadium lithium owing to have high reversible specific capacity, high charging/discharging voltage and stable structure, gets more and more people's extensive concerning.The average discharge platform of phosphoric acid vanadium lithium is about 4.0 V; In the voltage range of 3.0-5.0 V, theoretical capacity is 197 mAh/g, and reversible capacity is more than 170 mAh/g, and in the voltage range of 3.0-4.5 V, theoretical capacity is 133 mAh/g.Good cycle performance that it has and good security performance.
In recent years, the material of silicate series obtains extensive studies.The silicate material abundant raw materials, environmentally safe has excellent cyclical stability, thermal stability and fail safe, is a kind of new type lithium ion battery positive electrode that has development potentiality.People have carried out preliminary research to materials such as ferric metasilicate lithium, manganese silicate of lithium, cobaltous silicate lithium, silicic acid nickel lithiums.
Find that through retrieval application number is 200810117701.8, publication number is CN101339992A, and patent name is: a kind of preparation method's of lithium ionic cell positive electrode material vanadium lithium silicate patent of invention discloses SiO in its specification 4 4-Ion replaces Li 3V 2(PO 4) .3In PO 4 3-, obtain Li 6V 2(SiO 4) .3New material, the molecular weight of this material and Li 3V 2(PO 4) .3About the same, and, select phosphoric acid vanadium lithium Li for use because the cost of silicate material is lower than the cost of phosphate material 6V 2(SiO 4) .3Better to reducing the product cost effect, specific capacity is higher, but the compositing range of material is less, and the product line of producing is single relatively, is difficult to as required material be regulated and control into series of products.
Summary of the invention
The present invention provides a kind of specific capacity height, electric conductivity and good cycling stability for solving the technical problem that exists in the known technology, and the compositing range of material is wide, synthetic easily, can as required material be regulated and control into a kind of anode material for lithium-ion batteries of series of products and preparation method thereof.
The technical scheme that the present invention takes for the technical problem that exists in the solution known technology is:
1, a kind of anode material for lithium-ion batteries is characterized in: described material is Li 3+xV 2(PO 4) 3-x(SiO 4) x, 0≤x≤3 wherein.
2, a kind of preparation method of anode material for lithium-ion batteries, be characterized in: step comprises:
⑴ take by weighing raw material:
Take by weighing lithium source, vanadium source, phosphorus source, silicon source, wherein 0≤x≤3 by atomic molar than Li:V:P:Si=3+x:2:3-x:x; Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, the lithium oxalate; Described vanadium source is one or more in vanadic oxide or the metavanadic acid amine; Described phosphorus source is one or more in phosphoric acid, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate; Described silicon source is one or more in silicon dioxide or the tetraethoxysilane;
⑵ prepare gelatinous mixture:
Vanadium source among the step ⑴ is dissolved in aqueous hydrogen peroxide solution or the oxalic acid solution that concentration is 5-30 %, lithium source, phosphorus source, silicon source are added vanadium source solution, the 50-90 ℃ of heating and continuous formation gelatinous mixture that is stirred to;
⑶ prepare presoma:
Gelatinous mixture among the step ⑵ is inserted in the drying box 70-120 ℃ carried out dry 2-10 hour, obtain presoma;
⑷ prepare slurry:
Take by weighing carbon source and presoma by mass ratio 0.01-0.20, place ball grinder to mix, add 5-50 mL liquid phase ball-milling medium and carried out the liquid phase ball milling 2-24 hour, be prepared into slurry;
⑸ prepare Li 3+xV 2(PO 4) 3-x(SiO 4) xMaterial:
Place drying box to carry out 60-150 ℃ of dry 2-10 hour in the slurry of making among the step ⑷; pack into after the taking-up nitrogen, argon gas, in hydrogen-argon-mixed in a kind of or device of hydrogen nitrogen mixed gas as protective atmosphere; 700-900 ℃ of constant temperature sintering 4-48 hour; powered-down; behind the natural cooling, obtain the Li of 0≤x≤3 3+xV 2(PO 4) 3-x(SiO 4) xMaterial.
The present invention can also adopt following technical scheme:
The preparation method of anode material for lithium-ion batteries is characterized in that: the liquid phase ball-milling medium described in the step ⑷ is a kind of mixture in a kind of or water in isopropyl alcohol, ethanol, acetone, the water and isopropyl alcohol, ethanol, the acetone.
The preparation method of anode material for lithium-ion batteries is characterized in that: carbon source described in the step ⑷ is one or more in acetylene black, graphite, sucrose, glucose, citric acid, phenolic resins, pitch, the polyvinyl alcohol.
Advantage and good effect that the present invention has are:
The present invention is because with SiO 4 4-Ion partly replaces the PO in the phosphoric acid vanadium lithium 4 3-, not only theoretical specific capacity height, material structure are stablized, and security performance is good, and material is easier to be synthetic, has enlarged the compositing range of material, can as required material be regulated and control into series of products.
Description of drawings
Fig. 1 is the X-ray diffractogram of anode material for lithium-ion batteries of the present invention;
Fig. 2 is the cycle performance figure (0.1 C, 3-4.8 V) of anode material for lithium-ion batteries of the present invention.
Embodiment
For further understanding summary of the invention of the present invention, characteristics and effect, exemplify following examples now, and conjunction with figs. 1-2 is described in detail as follows:
A kind of anode material for lithium-ion batteries is Li 3+xV 2(PO 4) 3-x(SiO 4) x, 0≤x≤3 wherein.
The preparation method of anode material for lithium-ion batteries, step comprises:
⑴ take by weighing raw material:
Take by weighing lithium source, vanadium source, phosphorus source, silicon source, wherein 0≤x≤3 by atomic molar than Li:V:P:Si=3+x:2:3-x:x; Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, the lithium oxalate; Described vanadium source is one or more in vanadic oxide or the metavanadic acid amine; Described phosphorus source is one or more in phosphoric acid, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate; Described silicon source is one or more in silicon dioxide or the tetraethoxysilane;
⑵ prepare gelatinous mixture:
Vanadium source among the step ⑴ is dissolved in aqueous hydrogen peroxide solution or the oxalic acid solution that concentration is 5-30 %, lithium source, phosphorus source, silicon source are added vanadium source solution, the 50-90 ℃ of heating and continuous formation gelatinous mixture that is stirred to;
⑶ prepare presoma:
Gelatinous mixture among the step ⑵ is inserted in the drying box 70-120 ℃ carried out dry 2-10 hour, obtain presoma;
⑷ prepare slurry:
Take by weighing carbon source and presoma by mass ratio 0.01-0.20, place ball grinder to mix, add 5-50 mL liquid phase ball-milling medium and carried out the liquid phase ball milling 2-24 hour, be prepared into slurry; Described carbon source is one or more in acetylene black, graphite, sucrose, glucose, citric acid, phenolic resins, pitch, the polyvinyl alcohol; Described liquid phase ball-milling medium is a kind of mixture in a kind of or water in isopropyl alcohol, ethanol, acetone, the water and isopropyl alcohol, ethanol, the acetone.
⑸ prepare Li 3+xV 2(PO 4) 3-x(SiO 4) xMaterial:
Place drying box to carry out 60-150 ℃ of dry 2-10 hour in the slurry of making among the step ⑷; pack into after the taking-up nitrogen, argon gas, in hydrogen-argon-mixed in a kind of or device of hydrogen nitrogen mixed gas as protective atmosphere; 700-900 ℃ of constant temperature sintering 4-48 hour; powered-down; behind the natural cooling, obtain the Li of 0≤x≤3 3+xV 2(PO 4) 3-x(SiO 4) xMaterial.
Embodiment 1
Take by weighing Li respectively 2CO 31.594 gram, V 2O 55.512 gram, LiH 2PO 47.207 gram, SiO 21.275 gram, its atomic molar is than being Li:V:P:Si=3.7:2:2.3:0.7; With concentration is that hydrogen peroxide solution 50 mL of 15 % under agitation slowly are added to V 2O 5In the powder, form the colloidal solution of yellow swelling.With LiH 2PO 4Be dissolved in the 50 mL deionized waters Li 2CO 3Be dissolved in the aqueous citric acid solution of 20 mL, SiO 2Be dispersed in the 20 mL ethanol; Under magnetic agitation aforesaid colloid and solution are mixed, continuing to stir and control mixeding liquid temperature is 70 ℃, and solvent is evaporated gradually, forms the gelatinous mixture of stable homogeneous until mixed liquor.Gelatinous mixture is placed 90 ℃ of following dryings of drying box 6 hours, obtain presoma.Presoma and 5 gram glucose are mixed, change in the liquid phase ball grinder, add deionized water 20 mL again,, make slurry with 200 rev/mins rotating speed ball millings 6 hours; Slurry in 80 ℃ of dryings corundum crucible of packing into after 4 hours, is contained H in volume ratio 28% Ar/H 2Under the mixed atmosphere, kept 6 hours after rising to 800 ℃ with the heating rate of 1.5 ℃/min, powered-down behind the natural cooling, is made Li 3.7V 2(PO 4) 2.3(SiO 4) 0.7Material.Take by weighing the positive electrode of embodiment 1 gained respectively with the mass ratio of 83:10:7: acetylene black: the mixed slurry that gets of PVdF (Kynoar), evenly be coated on the Al collector and dry, the positive plate of the about 100 μ m of thickness is made in roll extrusion.Selecting metal lithium sheet for use is negative pole, and Celgard 2300 is a barrier film, and electrolyte is that concentration is the LiPF of 1.0 M 6/ EC+DEC+DMC (volume ratio 1:1:1), the assembling button cell.
Embodiment 2
Take by weighing Li respectively 2CO 31.371 gram, NH 4VO 33.510 gram, LiH 2PO 47.520 gram, TEOS 3.863 gram, its atomic molar be than Li:V:P:Si=3.6:2:2.4:0.6, under agitation, and with NH 4VO 3Be dissolved in the oxalic acid deionized water solution that 50 mL concentration are 10 %.With LiH 2PO 4Be dissolved in the 20 mL deionized waters Li 2CO 3Being dissolved in 20 mL concentration is in the aqueous citric acid solution of 10 %, and TEOS is dispersed in the 20 mL ethanol; Under magnetic agitation aforesaid solution is mixed, continuing to stir and control mixeding liquid temperature is 60 ℃, forms the gelatinous mixture of stable homogeneous until mixed liquor; Gelatinous mixture is placed 100 ℃ of following dryings of drying box 4 hours, obtain presoma.Presoma and 1 gram pitch are mixed, change in the liquid phase ball grinder, add ethanol 20 mL again,, make slurry with 220 rev/mins rotating speed ball millings 5 hours; Place drying box to carry out 90 ℃ of dryings 4 hours in slurry, the corundum crucible of packing into after the taking-up in Ar gas, kept 4 hours after rising to 900 ℃ with the heating rate of 3.0 ℃/min, and powered-down behind the natural cooling, is made Li 3.6V 2(PO 4) 2.4(SiO 4) 0.6Material.
Embodiment 3
Take by weighing LiOHH respectively 2O0.057 gram, V 2O 53.737 gram, Li 3PO 42.32 gram, TEOS 3.863 grams, its atomic molar compares Li:V:P:Si=3.05:2:2.95:0.05; Under agitation, with V 2O 5Be dissolved in the oxalic acid deionized water solution that 50 mL concentration are 10 %; Respectively with Li 3PO 4Be dissolved in 20 mL deionized waters, LiOHH 2O be dissolved in 50 mL deionized water, be dispersed in TEOS in the 20 mL ethanol after, all insert under the magnetic agitation in the described aqueous solution, continue to stir and the control mixeding liquid temperature is 65 ℃, form the gelatinous mixture of stable homogeneous until mixed liquor.Gelatinous mixture is placed 120 ℃ of following dryings of drying box 2 hours, obtain presoma.Presoma and 2 gram polyvinyl alcohol are mixed evenly, change in the liquid phase ball grinder, add acetone 20 mL again,, make slurry with 250 rev/mins rotating speed ball millings 4 hours.Place drying box to carry out 120 ℃ of dryings corundum crucible of packing into after 3 hours in slurry, contain H in volume ratio 28% Ar/H 2Under the mixed atmosphere, kept 16 hours after rising to 700 ℃ with the heating rate of 2.0 ℃/min, powered-down behind the natural cooling, is made Li 3.05V 2(PO 4) 2.95(SiO 4) 0.05Material.
Zhi Bei anode material for lithium-ion batteries combines the advantage of phosphate and silicate according to the method described above, specific capacity original text not only, cyclical stability is better, security performance is good, and material is easier to be synthetic, enlarge the compositing range of material, can as required material have been regulated and control into series of products, be expected to become high-capacity lithium ion cell positive electrode of new generation.

Claims (4)

1. anode material for lithium-ion batteries, it is characterized in that: described material is Li 3+xV 2(PO 4) 3-x(SiO 4) x, 0≤x≤3 wherein.
2. the preparation method of an anode material for lithium-ion batteries, it is characterized in that: step comprises:
⑴ take by weighing raw material:
Take by weighing lithium source, vanadium source, phosphorus source, silicon source, wherein 0≤x≤3 by atomic molar than Li:V:P:Si=3+x:2:3-x:x; Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, the lithium oxalate; Described vanadium source is one or more in vanadic oxide or the metavanadic acid amine; Described phosphorus source is one or more in phosphoric acid, lithium phosphate, lithium dihydrogen phosphate, phosphoric acid hydrogen two lithiums, ammonium phosphate, ammonium dihydrogen phosphate, the diammonium hydrogen phosphate; Described silicon source is one or more in silicon dioxide or the tetraethoxysilane;
⑵ prepare gelatinous mixture:
Vanadium source among the step ⑴ is dissolved in aqueous hydrogen peroxide solution or the oxalic acid solution that concentration is 5-30 %, lithium source, phosphorus source, silicon source are added vanadium source solution, the 50-90 ℃ of heating and continuous formation gelatinous mixture that is stirred to;
⑶ prepare presoma:
Gelatinous mixture among the step ⑵ is inserted in the drying box 70-120 ℃ carried out dry 2-10 hour, obtain presoma;
⑷ prepare slurry:
Take by weighing carbon source and presoma by mass ratio 0.01-0.20, place ball grinder to mix, add 5-50 mL liquid phase ball-milling medium and carried out the liquid phase ball milling 2-24 hour, be prepared into slurry;
⑸ prepare Li 3+xV 2(PO 4) 3-x(SiO 4) xMaterial:
Place drying box to carry out 60-150 ℃ of dry 2-10 hour in the slurry of making among the step ⑷; pack into after the taking-up nitrogen, argon gas, in hydrogen-argon-mixed in a kind of or device of hydrogen nitrogen mixed gas as protective atmosphere; 700-900 ℃ of constant temperature sintering 4-48 hour; powered-down; behind the natural cooling, obtain the Li of 0≤x≤3 3+xV 2(PO 4) 3-x(SiO 4) xMaterial.
3. the preparation method of anode material for lithium-ion batteries according to claim 2 is characterized in that: the liquid phase ball-milling medium described in the step ⑷ is a kind of mixture in a kind of or water in isopropyl alcohol, ethanol, acetone, the water and isopropyl alcohol, ethanol, the acetone.
4. the preparation method of anode material for lithium-ion batteries according to claim 2, it is characterized in that: carbon source described in the step ⑷ is one or more in acetylene black, graphite, sucrose, glucose, citric acid, phenolic resins, pitch, the polyvinyl alcohol.
CN2011102047935A 2011-07-21 2011-07-21 Lithium ion cell anode material and preparation method thereof Pending CN102290575A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102903919A (en) * 2012-10-23 2013-01-30 中国科学院过程工程研究所 Anode material lithium vanadium silicate for lithium ion battery, preparation method and application of anode material
WO2024032508A1 (en) * 2022-08-10 2024-02-15 比亚迪股份有限公司 Positive electrode active material, and preparation method therefor and use thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514640B1 (en) * 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
CN101339992A (en) * 2008-08-04 2009-01-07 清华大学 Preparation of lithium ionic cell positive electrode material vanadium lithium silicate
CN101841024A (en) * 2010-03-11 2010-09-22 南昌大学 Method for preparing cathode material lithium vanadium phosphate of lithium ion battery by using fast sol-gel method
CN101955176A (en) * 2010-10-20 2011-01-26 河南联合新能源有限公司 Method for preparing anode material lithium vanadium phosphate of lithium ion battery by microwave sintering

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6514640B1 (en) * 1996-04-23 2003-02-04 Board Of Regents, The University Of Texas System Cathode materials for secondary (rechargeable) lithium batteries
CN101339992A (en) * 2008-08-04 2009-01-07 清华大学 Preparation of lithium ionic cell positive electrode material vanadium lithium silicate
CN101841024A (en) * 2010-03-11 2010-09-22 南昌大学 Method for preparing cathode material lithium vanadium phosphate of lithium ion battery by using fast sol-gel method
CN101955176A (en) * 2010-10-20 2011-01-26 河南联合新能源有限公司 Method for preparing anode material lithium vanadium phosphate of lithium ion battery by microwave sintering

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102903919A (en) * 2012-10-23 2013-01-30 中国科学院过程工程研究所 Anode material lithium vanadium silicate for lithium ion battery, preparation method and application of anode material
CN102903919B (en) * 2012-10-23 2015-09-30 中国科学院过程工程研究所 A kind of lithium ionic cell positive electrode material vanadium lithium silicate, preparation method and its usage
WO2024032508A1 (en) * 2022-08-10 2024-02-15 比亚迪股份有限公司 Positive electrode active material, and preparation method therefor and use thereof

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Application publication date: 20111221