CN102569798A - Regeneration method of lithium iron silicate lithium ion battery anode material - Google Patents

Regeneration method of lithium iron silicate lithium ion battery anode material Download PDF

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Publication number
CN102569798A
CN102569798A CN2012100222703A CN201210022270A CN102569798A CN 102569798 A CN102569798 A CN 102569798A CN 2012100222703 A CN2012100222703 A CN 2012100222703A CN 201210022270 A CN201210022270 A CN 201210022270A CN 102569798 A CN102569798 A CN 102569798A
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lithium
anode material
iron silicate
ion batteries
lithium iron
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邓超
张森
孙言虹
马丽
董哲
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Harbin Normal University
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Harbin Normal University
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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

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Abstract

The invention discloses a regeneration method of a lithium iron silicate lithium ion battery anode material and relates to a regeneration method of a composite material. The regeneration method of a lithium iron silicate lithium ion battery anode material solves the problem that bivalent iron of a lithium iron silicate material can be oxidized easily to ferric iron so that electrochemical performances of the lithium iron silicate material are reduced. The regeneration method of a lithium iron silicate lithium ion battery anode material comprises the following steps of 1, carrying out ball milling of oxidized lithium iron silicate and a carbon-containing organic matter, and 2, sintering products obtained by the step 1 at a temperature of 500 to 700 DEG C in a protective gas atmosphere for 0.5 to 10 hours to realize regeneration of a lithium iron silicate lithium ion battery anode material. Through the regeneration method provided by the invention, an internal structure and a surface condition of oxidized lithium iron silicate can be effectively improved and electrochemical performances of the oxidized lithium iron silicate can be recovered. The regeneration method provided by the invention is simple and convenient, has high operation safety, is very suitable for material batch processing and industrial production, and effectively solves the problem that a lithium iron silicate material cannot be stored easily, can be oxidized easily and has poor performances after being oxidized.

Description

The renovation process of ferric metasilicate lithium anode material for lithium-ion batteries
Technical field
The present invention relates to a kind of renovation process of composite material.
Background technology
The ferric metasilicate lithium material is a kind of in the silicate-base electrode material.It is a kind of novel electrode material that development in recent years is got up; Characteristics such as it has that with low cost, environmental protection, security performance are good, Stability Analysis of Structures, chemical property are better; Receive the researcher and paid attention to widely, become one of the most potential anode material for lithium-ion batteries.But the ferro element in the ferric metasilicate lithium material is a ferrous iron, in storage process, is very easy to be oxidized to higher valence state.More impurity is contained in ferric metasilicate lithium inside after the oxidation, the surface coverage oxide-film, and its chemical property significantly descends.
Summary of the invention
The ferro element that the present invention will solve in the ferric metasilicate lithium material is that ferrous iron is oxidized to higher valence state easily, causes the technical problem of its chemical property decline, and a kind of renovation process of ferric metasilicate lithium anode material for lithium-ion batteries is provided.
The renovation process step of ferric metasilicate lithium anode material for lithium-ion batteries of the present invention is following:
One, with the ferric metasilicate lithium after the oxidation and carbonaceous organic material according to 1: 0.01～10 mixed in molar ratio after under inert gas shielding, ball milling 0.1～6 hour, wherein ratio of grinding media to material is 10: 1;
Two, with the product of step 1 gained sintering 0.5～10 hour under 500 ℃～700 ℃, the condition of protection gas shiled, promptly accomplish the regeneration of ferric metasilicate lithium anode material for lithium-ion batteries; Protection gas described in the step 2 is the mist that nitrogen, argon gas or nitrogen and hydrogen are formed according to 1: 0.05～2 mol ratio; Carbonaceous organic material described in the step 1 is Citric Acid Mono, sucrose, glucose or starch; Inert gas described in the step 1 is nitrogen or argon gas.
Can effectively improve the internal structure and the surface state of oxidation ferric metasilicate lithium through renovation process of the present invention, recover its chemical property.Regeneration techniques of the present invention is simple and convenient, and processing safety is high, is fit to very much the batch process and the suitability for industrialized production of material, and efficiently solve the ferric metasilicate lithium material be not easy to store, be prone to oxidized, the problem of decreased performance after the oxidation.
Description of drawings
Fig. 1 is the XRD figure of the experiment one mesosilicic acid iron lithium ion battery positive electrode of embodiment three; Fig. 2 is the XRD figure of the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation in the experiment one of embodiment three; Fig. 3 is the XRD figure of the ferric metasilicate lithium anode material for lithium-ion batteries after the regeneration in the experiment one of embodiment three; Fig. 4 is the experiment one discharge capacity figure of mesosilicic acid iron lithium ion battery positive electrode under different discharge-rates of embodiment three; Fig. 5 is the discharge capacity figure of ferric metasilicate lithium anode material for lithium-ion batteries under different discharge-rates after the oxidation in the experiment one of embodiment three; Fig. 6 is the discharge capacity figure of ferric metasilicate lithium anode material for lithium-ion batteries under different discharge-rates after the regeneration in the experiment one of embodiment three.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the renovation process step of this execution mode mesosilicic acid iron lithium ion battery positive electrode is following:
One, with the ferric metasilicate lithium after the oxidation and carbonaceous organic material according to 1: 0.01～10 mixed in molar ratio after under inert gas shielding; Ball milling 0.1～6 hour, wherein ratio of grinding media to material is 10: 1 (mass ratio of the ferric metasilicate lithium after the oxidation and the gross mass of carbonaceous organic material and abrading-ball is 1: 10);
Two, with the product of step 1 gained sintering 0.5～10 hour under 500 ℃～700 ℃, the condition of protection gas shiled, promptly accomplish the regeneration of ferric metasilicate lithium anode material for lithium-ion batteries; Protection gas described in the step 2 is the mist that nitrogen, argon gas or nitrogen and hydrogen are formed according to 1: 0.05～2 mol ratio.
Embodiment two: what this execution mode and embodiment one were different is that the carbonaceous organic material described in the step 1 is Citric Acid Mono, sucrose, glucose or starch.Other is identical with embodiment one.
Embodiment three: what this execution mode was different with one of embodiment one or two is that the inert gas described in the step 1 is nitrogen or argon gas.Other is identical with one of embodiment one or two.
Adopt following experimental verification effect of the present invention:
Experiment one:
One, with 2.04g CH 3COOLi2H 2O, 3.35g FeC 6H 5O 75H 2O, 2.1g C 6H 8O 7H 2O and 0.06gSiO 2Adopt ball milling (ratio of grinding media to material of ball milling is 10: 1) evenly to mix 8 hours,, obtain black powder, be the ferric metasilicate lithium anode material for lithium-ion batteries products therefrom sintering 8 hours under 600 ℃, hydrogen atmosphere;
Two, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Three, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 1.0g C 6H 8O 7H 2O is under the nitrogen atmosphere protection, and ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 6 hours;
Four, with the product of step 3 sintering 2 hours under 600 ℃, argon shield, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.
Contrasted visiblely by Fig. 1, Fig. 2 and Fig. 3 three width of cloth figure, the spectrogram diffraction maximum of ferric metasilicate lithium anode material for lithium-ion batteries is sharp-pointed, but ferric metasilicate lithium anode material for lithium-ion batteries diffraction maximum seriously undermines after the oxidation.The diffraction maximum of regeneration back ferric metasilicate lithium anode material for lithium-ion batteries is restored.Explain that ferric metasilicate lithium anode material for lithium-ion batteries internal structure and surface state have all produced bigger variation after the oxidation.And behind the employing regeneration techniques, the structure of ferric metasilicate lithium anode material for lithium-ion batteries has obtained recovery.
Visible by Fig. 4, Fig. 5 and Fig. 6, the electrochemistry capacitance of ferric metasilicate lithium anode material for lithium-ion batteries significantly descends after the oxidation.And regeneration back ferric metasilicate lithium anode material for lithium-ion batteries discharge capacity has obtained recovery.Therefore, the regeneration techniques that the present invention relates to can have the chemical property of efficient recovery material.
Experiment two:
One, with 2.04g CH 3COOLi2H 2O, 3.35g FeC 6H 5O 75H 2O, 2.1g C 6H 8O 7H 2O and 0.06gSiO 2Adopt ball milling (ratio of grinding media to material of ball milling is 10: 1) evenly to mix 8 hours, under 600 ℃, sintering is 8 hours under the hydrogen atmosphere, obtains black powder, is the ferric metasilicate lithium anode material for lithium-ion batteries with the product of gained.
Two, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Three, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 2.0g C 12H 22O 11Under the argon gas atmosphere protection, ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 6 hours;
Four, with the product of step 3 sintering 2 hours under 600 ℃, argon shield, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.
Experiment three:
One, with 2.04g CH 3COOLi2H 2O, 3.35g FeC 6H 5O 75H 2O, 2.1g C 6H 8O 7H 2O and 0.06gSiO 2Adopt ball milling (ratio of grinding media to material of ball milling is 10: 1) evenly to mix 8 hours, with product under 600 ℃, sintering is 8 hours under the hydrogen atmosphere, obtains black powder, is the ferric metasilicate lithium anode material for lithium-ion batteries;
Two, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Three, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 2.0g C 12H 22O 11Under the nitrogen atmosphere protection, ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 2 hours;
Four, with the product of step 3 sintering 4 hours under 700 ℃, nitrogen and hydrogen mixed gas atmosphere (nitrogen and hydrogen mol ratio are 1: 0.1) protection, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.
Experiment four:
One, with 2.04g CH 3COOLi2H 2O, 3.35g FeC 6H 5O 75H 2O and 2.1gC 6H 8O 7H 2O is dissolved in the 100mL water, processes solution 1;
Two, with 2.08g C 8H 20O 4Si and 1gCH 3Put into agitated reactor after COOH (mass concentration is 30%) is dissolved in the 100mL water, at 70 ℃, nitrogen gas protection down, carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds, formation solution 2 then;
Three, solution 1 is poured in the solution 2, in nitrogen protection, to keep-up pressure to 0.4MPa, temperature be under 80 ℃ the condition, the rotating speed that continues with 100 rev/mins stirred 6 hours, formed colloidal sol 3;
Four, with colloidal sol 3 be at 100 ℃, vacuum degree-condition of 0.1MPa under dry 24 hours, then products therefrom is ground, obtain precursor powder;
Five, with precursor powder sintering 8 hours under 600 ℃, hydrogen atmosphere, obtain black powder, promptly get ferric metasilicate lithium cell positive material with multilayer classifying structure;
Six, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Seven, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 2.0g C 12H 22O 11Under the nitrogen atmosphere protection, ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 2 hours;
Eight, with the product of step 3 sintering 4 hours under 700 ℃, nitrogen and hydrogen mixed gas atmosphere (nitrogen and hydrogen mol ratio are 1: 0.1) protection, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.
Experiment five:
One, with 2.04g CH 3COOLi2H 2O, 3.35g FeC 6H 5O 75H 2O and 3.42g C 12H 22O 11Be dissolved in the 100mL water, process solution 1;
Two, with 2.08g C 8H 20O 4Si and 1gCH 3Put into agitated reactor after COOH (mass concentration is 30%) is dissolved in the 100mL water, at 70 ℃, nitrogen gas protection down, carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds, formation solution 2 then;
Three, solution 1 is poured in the solution 2, in nitrogen protection, to keep-up pressure to 0.4MPa, temperature be under 80 ℃ the condition, the rotating speed that continues with 100 rev/mins stirred 6 hours, formed colloidal sol 3;
Four, with colloidal sol 3 be at 100 ℃, vacuum degree-condition of 0.1MPa under dry 24 hours, then products therefrom is ground, obtain precursor powder;
Five, with precursor powder sintering 8 hours under 600 ℃, hydrogen atmosphere, obtain black powder, promptly get ferric metasilicate lithium cell positive material with multilayer classifying structure;
Six, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Seven, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 2.0g C 12H 22O 11Under the nitrogen atmosphere protection, ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 2 hours;
Eight, with the product of step 3 sintering 4 hours under 700 ℃, nitrogen protection, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.
Experiment six:
One, with 2.04g CH 3COOLi2H 2O, 2.45g Mn (CH 3COO) 24H 2O and 2.1g C 6H 8O 7H 2O is dissolved in the 100mL water, processes solution 1;
Two, with 2.08g C 8H 20O 4Si and 1gCH 3Put into agitated reactor after COOH (mass concentration is 30%) is dissolved in the 100mL water, at 70 ℃, nitrogen gas protection down, carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds, formation solution 2 then;
Three, solution 1 is poured in the solution 2, in nitrogen protection, to keep-up pressure to 0.2MPa, temperature be under 80 ℃ the condition, the rotating speed that continues with 100 rev/mins stirred 6 hours, formed colloidal sol 3;
Four, with colloidal sol 3 be at 100 ℃, vacuum degree-condition of 0.1MPa under dry 24 hours, then products therefrom is ground, obtain precursor powder;
Five, with precursor powder sintering 8 hours under 600 ℃, hydrogen atmosphere, obtain black powder, promptly get silicate-base cell positive material with multilayer classifying structure;
Six, the ferric metasilicate lithium anode material for lithium-ion batteries was placed in the air 60 days, obtains the ferric metasilicate lithium anode material for lithium-ion batteries after the oxidation;
Seven, with ferric metasilicate lithium anode material for lithium-ion batteries after the 1.0g oxidation and 2.0g C 12H 22O 11Under the nitrogen atmosphere protection, ball milling (ratio of grinding media to material of ball milling is 10: 1) ground 2 hours;
Eight, with the product of step 3 sintering 4 hours under 700 ℃, argon shield, the ferrosilite anode material for lithium-ion batteries after can obtaining regenerating.

Claims (3)

1. the renovation process of ferric metasilicate lithium anode material for lithium-ion batteries is characterized in that the renovation process step of ferric metasilicate lithium anode material for lithium-ion batteries is following:
One, with the ferric metasilicate lithium after the oxidation and carbonaceous organic material according to 1: 0.01～10 mixed in molar ratio after under inert gas shielding, ball milling 0.1～6 hour, wherein ratio of grinding media to material is 10: 1;
Two, with the product of step 1 gained sintering 0.5～10 hour under 500 ℃～700 ℃, the condition of protection gas shiled, promptly accomplish the regeneration of ferric metasilicate lithium anode material for lithium-ion batteries; Protection gas described in the step 2 is the mist that nitrogen, argon gas or nitrogen and hydrogen are formed according to 1: 0.05～2 mol ratio.
2. according to the renovation process of the said ferric metasilicate lithium anode material for lithium-ion batteries of claim 1, it is characterized in that the carbonaceous organic material described in the step 1 is Citric Acid Mono, sucrose, glucose or starch.
3. according to the renovation process of claim 1 or 2 said ferric metasilicate lithium anode material for lithium-ion batteries, it is characterized in that the inert gas described in the step 1 is nitrogen or argon gas.
CN2012100222703A 2012-02-01 2012-02-01 Regeneration method of lithium iron silicate lithium ion battery anode material Pending CN102569798A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104425819B (en) * 2013-09-09 2016-06-29 国家纳米科学中心 A kind of preparation method of the ferric metasilicate lithium as anode material for lithium-ion batteries

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101582526A (en) * 2009-06-25 2009-11-18 复旦大学 Reparative regeneration method of inactive ferrous phosphate lithium battery anode material
CN101626073A (en) * 2008-08-25 2010-01-13 中南大学 Method and device for preventing oxidation in synthesis of anode material of lithium-ion battery
CN101847763A (en) * 2010-04-09 2010-09-29 奇瑞汽车股份有限公司 Comprehensive recovering method of waste lithium iron phosphate battery
CN102064366A (en) * 2010-11-08 2011-05-18 杭州东建能源科技有限公司 Regeneration method for lithium iron phosphate

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101626073A (en) * 2008-08-25 2010-01-13 中南大学 Method and device for preventing oxidation in synthesis of anode material of lithium-ion battery
CN101582526A (en) * 2009-06-25 2009-11-18 复旦大学 Reparative regeneration method of inactive ferrous phosphate lithium battery anode material
CN101847763A (en) * 2010-04-09 2010-09-29 奇瑞汽车股份有限公司 Comprehensive recovering method of waste lithium iron phosphate battery
CN102064366A (en) * 2010-11-08 2011-05-18 杭州东建能源科技有限公司 Regeneration method for lithium iron phosphate

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104425819B (en) * 2013-09-09 2016-06-29 国家纳米科学中心 A kind of preparation method of the ferric metasilicate lithium as anode material for lithium-ion batteries

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Application publication date: 20120711