CN102569799A - Method for preparing silicate-based composite material with multilevel hierarchical structure - Google Patents

Method for preparing silicate-based composite material with multilevel hierarchical structure Download PDF

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CN102569799A
CN102569799A CN2012100223015A CN201210022301A CN102569799A CN 102569799 A CN102569799 A CN 102569799A CN 2012100223015 A CN2012100223015 A CN 2012100223015A CN 201210022301 A CN201210022301 A CN 201210022301A CN 102569799 A CN102569799 A CN 102569799A
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solution
silicate
composite material
lithium salts
classifying structure
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邓超
张森
林惠明
孙言虹
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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

Abstract

The invention discloses a method for preparing a silicate-based composite material with a multilevel hierarchical structure and relates to a method for preparing a positive pole material of a cell. The invention aims to solve the technical problems of reduction of magnification charge-discharge property, low tap density and low filling density of the existing silicate-based material, which are caused by single granularity of the existing silicate-based material. The method comprises the following steps: dissolving lithium salts, transition metal salts and a carbon-containing organic matter into distilled water at room temperature to form a solution 1; after dissolving tetraethoxysilane and acetic acid into the distilled water, placing the obtained solution into a reaction kettle to prepare a solution 2; pouring the solution 1 into the solution 2 and stirring to form sol 3; and drying and grinding the sol 3 and then sintering to obtain black powder, i.e., a target product. Materials prepared by adopting the method disclosed by the invention are particles with a micron-level multilevel hierarchical structure and a nano-level multilevel hierarchical structure. By adoption of the multilevel hierarchical structure, the normal transmission of lithium ions is ensured and the tap density and the filling density of the material are also kept, so that the electrochemical capacity of the material is improved.

Description

Preparation method with silicate-base composite material of multilayer classifying structure
Technical field
The present invention relates to a kind of preparation method of cell positive material.
Background technology
The grain structure of electrode material is the key factor that influences its performance.The particle diameter of micron particles is bigger, usually greater than 1 micron.This big granularity makes the electrochemistry the evolving path of lithium ion in material longer, has reduced the transfer ability of ion, causes the rate charge-discharge decreased performance of material.The granularity of nano-scale particle is less, is generally 10 nanometers～hundreds of nanometer.Smaller particle size effectively reduces the migration distance of ion, thereby has improved the rate charge-discharge ability of material.But the tap density and the packed density of nanometer materials are lower, have influenced the overall capacity of battery.In addition, nano-scale particle has very large specific area, and the contact area of electrolyte and material is very big, thereby causes the cycle performance of material to reduce, and influences the overall performance of battery.
Silicate-based material 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 granularity of present silicate-based material of synthesizing single (being merely nanoscale or micron order) influences the raising of its combination property.
Summary of the invention
The present invention will solve the lower technical problem of rate charge-discharge decreased performance, tap density and packed density that the granularity single (being merely nanoscale or micron order) that has silicate-based material now causes material, and a kind of preparation method with silicate-base composite material of multilayer classifying structure is provided.
The preparation method that the present invention has the silicate-base cell positive material of multilayer classifying structure is undertaken by following step:
One, according to chemical formula Li 2MSiO 4, be that 2: 1: 1 ratio takes by weighing lithium salts, transition metal salt and tetraethoxysilane respectively according to Li element, M element and Si element mol ratio;
Two, at room temperature be dissolved in lithium salts, transition metal salt and carbonaceous organic material in the distilled water; Form solution 1; The mol ratio of carbonaceous organic material and lithium salts is 1: 0.05～5, and the mol ratio of lithium salts and transition metal salt is 2: 1, and the concentration of lithium salts is 0.01mol/L～5mol/L in the solution 1;
Three, put into agitated reactor after being dissolved in the distilled water according to 1: 0.01～4 mol ratio tetraethoxysilane and acetate; Then under 70 ℃, inert gas shielding; Carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds; Form solution 2, the concentration of tetraethoxysilane is 0.01mol/L～5mol/L in the solution 2;
Four, according to solution 1 and solution 2 be 1: 0.1～3 volume ratio with solution 1 to going in the solution 2; At the pressure of inert gas shielding, reaction system is that 0.02MPa～1MPa, temperature are under 60 ℃～120 ℃ the condition; Continuation was stirred 6 hours with 100 rev/mins rotating speed, formed colloidal sol 3;
Five, 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;
Six, with precursor powder sintering 8 hours under 600 ℃～900 ℃, hydrogen atmosphere, obtain black powder, promptly get silicate-base cell positive material with multilayer classifying structure; M in the step 1 is Mn, Fe, Co or Ni; Lithium salts described in the step 1 is two water lithium acetates; Transition metal salt described in the step 1 is four water acetic acid manganese, Cobalt diacetate tetrahydrate, four water acetic acid nickel or five hydration ironic citrates; Carbonaceous organic material described in the step 2 is Citric Acid Mono, sucrose, glucose or starch; Inert gas described in the step 3 is nitrogen or argon gas; Inert gas described in the step 4 is nitrogen or argon gas.
The particle that the silicate-based material with multilayer classifying structure of employing the inventive method gained has micron and two kinds of rank multilayer classifyings of nanometer structure.Nano level particle grain size has guaranteed the normal transmission of lithium ion between 50nm～80nm.Micron particles has some nano-scale particles to constitute, and granularity is at 5 μ m～10 μ m.This bigger particle has kept the tap density and the packed density of material preferably, thereby has improved the electrochemistry capacitance of material.In a word, this structure had both kept the good dynamics performance of less nano-scale particle in the material, was interconnected to form micron particles through it again, had improved the physical property of material.The special compound mode of this nano-scale particle and micron particles has constituted the 3-d modelling of the multilayer classifying structure of silicate-base cell positive material uniqueness, thereby has effectively improved its electrochemistry combination property.
Description of drawings
Fig. 1 is the micron particles shape appearance figure that embodiment six experiments one gained has the ferric metasilicate lithium cell positive material of multilayer classifying structure; Fig. 2 is the nano-scale particle shape appearance figure that gained has the ferric metasilicate lithium cell positive material of multilayer classifying structure in embodiment six experiments one; Fig. 3 is the XRD spectra that gained has the ferric metasilicate lithium cell positive material of multilayer classifying structure in embodiment six experiments one; Fig. 4 is the 0.1C multiplying power discharging curve that gained has the ferric metasilicate lithium cell positive material of multilayer classifying structure in embodiment six experiments one; Fig. 5 is the discharge capacity correlation curve figure under different multiplying that gained has the ferric metasilicate lithium cell positive material of multilayer classifying structure in embodiment six experiments one; Fig. 6 is the discharge capacity under different discharging currents of gained ferric metasilicate lithium cell positive material in embodiment six experiments five.
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 preparation method that this execution mode has the silicate-base cell positive material of multilayer classifying structure is undertaken by following step:
One, according to chemical formula Li 2MSiO 4, be that 2: 1: 1 ratio takes by weighing lithium salts, transition metal salt and tetraethoxysilane respectively according to Li element, M element and Si element mol ratio;
Two, at room temperature be dissolved in lithium salts, transition metal salt and carbonaceous organic material in the distilled water; Form solution 1; The mol ratio of carbonaceous organic material and lithium salts is 1: 0.05～5, and the mol ratio of lithium salts and transition metal salt is 2: 1, and the concentration of lithium salts is 0.01mol/L～5mol/L in the solution 1;
Three, put into agitated reactor after being dissolved in the distilled water according to 1: 0.01～4 mol ratio tetraethoxysilane and acetate; Then under 70 ℃, inert gas shielding; Carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds; Form solution 2, the concentration of tetraethoxysilane is 0.01mol/L～5mol/L in the solution 2;
Four, according to solution 1 and solution 2 be 1: 0.1～3 volume ratio with solution 1 to going in the solution 2; At the pressure of inert gas shielding, reaction system is that 0.02MPa～1MPa, temperature are under 60 ℃～120 ℃ the condition; Continuation was stirred 6 hours with 100 rev/mins rotating speed, formed colloidal sol 3;
Five, 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;
Six, with precursor powder sintering 8 hours under 600 ℃～900 ℃, hydrogen atmosphere, obtain black powder, promptly get silicate-base cell positive material with multilayer classifying structure; M in the step 1 is Mn, Fe, Co or Ni.
Embodiment two: what this execution mode and embodiment one were different is that lithium salts described in the step 1 is two water lithium acetates.Other is identical with embodiment one.
Embodiment three: what this execution mode was different with one of embodiment one or two is that transition metal salt described in the step 1 is four water acetic acid manganese, Cobalt diacetate tetrahydrate, four water acetic acid nickel or five hydration ironic citrates.Other is identical with one of embodiment one or two.
Embodiment four: what this execution mode was different with one of embodiment one to three is that carbonaceous organic material described in the step 2 is Citric Acid Mono, sucrose, glucose or starch.Other is identical with one of embodiment one to three.
Embodiment five: what this execution mode was different with one of embodiment one to four is that inert gas described in the step 3 is nitrogen or argon gas.Other is identical with one of embodiment one to four.
Embodiment six: what this execution mode was different with one of embodiment one to five is that inert gas described in the step 4 is nitrogen or argon gas.Other is identical with one of embodiment one to five.
Adopt following experimental verification effect of the present invention:
Test one: 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.
With this experiment gained positive electrode, acetylene black and polyvinylidene fluoride according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was than ball mill mixing 5 hours; Then mixture is coated in that to use mass concentration be that 95% ethanol cleaned on three times the aluminium foil; The aluminium foil that will scribble mixture is again dried under 100 ℃ condition, the moulding of 20MPa pressed, promptly obtains positive pole.Adopt LiPF then 6Concentration is that the EC/DMC solution of 1mol/L is electrolyte, is assembled into the CR2032 button cell, on new prestige battery test system, carries out the test of constant current impulse electricity, and the test voltage interval is 1.5V～4.8V.
The used ball mill of this experiment is the planetary ball mill of the QM-3SP04 of Nanjing Univ. Instrument Factory's production.
Visible by Fig. 1 and Fig. 2, the material that this experiment is synthesized has micron particles, and its granularity is 10 μ m.Micron particles constitutes its granularity jointly by some nano-scale particles and is about 50nm～80nm.Therefore, the material that is synthesized has the multilayer classifying structure.Visible by Fig. 3, the material of this Experiment Preparation has good phase structure.But the heavy-current discharge capacity that is contrasted the positive electrode of knowledge capital implementation method preparation by Fig. 6 and Fig. 5 is significantly higher than the material that solid phase method prepares, and the chemical property of the material that the method for illustrative experiment one is prepared is compared with the electrode material that adopts the solid phase method preparation (testing five) and is significantly increased.
Test two: 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.
With this experiment gained positive electrode, acetylene black and polyvinylidene fluoride according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was than ball mill mixing 5 hours; Then mixture is coated in 95% ethanol and cleaned on three times the aluminium foil; The aluminium foil that will scribble mixture is again dried under 100 ℃ condition, the moulding of 20MPa pressed, promptly obtains positive pole.
The material that this experiment is synthesized has micron particles, and its granularity is 5 μ m.Micron particles constitutes its granularity jointly by some nano-scale particles and is about 50nm～80nm.Therefore, the material that is synthesized has the multilayer classifying structure.
Test three: 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.
With this experiment gained positive electrode, acetylene black and polyvinylidene fluoride according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was than ball mill mixing 5 hours; Then mixture is coated in 95% ethanol and cleaned on three times the aluminium foil; The aluminium foil that will scribble mixture is again dried under 100 ℃ condition, the moulding of 20MPa pressed, promptly obtains positive pole.
The material that this experiment is synthesized has micron particles, and its granularity is 6 μ m.Micron particles constitutes its granularity jointly by some nano-scale particles and is about 50nm～80nm.Therefore, the material that is synthesized has the multilayer classifying structure.
Test four: one, with 2.04g CH 3COOLi2H 2O, 2.49g Co (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.
With this experiment gained positive electrode, acetylene black and polyvinylidene fluoride according to positive electrode: acetylene black: polyvinylidene fluoride is that 80: 10: 10 quality was than ball mill mixing 5 hours; Then mixture is coated in 95% ethanol and cleaned on three times the aluminium foil; The aluminium foil that will scribble mixture is again dried under 100 ℃ condition, the moulding of 20MPa pressed, promptly obtains positive pole.
The material that this experiment is synthesized has micron particles, and its granularity is 8 μ m.Micron particles constitutes its granularity jointly by some nano-scale particles and is about 50nm～80nm.Therefore, the material that is synthesized has the multilayer classifying structure.
Experiment five:
The method that solid phase method prepares electrode material is following:
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 electrode material.
This execution mode adopts the electrode material of solid phase method preparation only to have micron particles.

Claims (6)

1. the preparation method who has the silicate-base composite material of multilayer classifying structure, the preparation method who it is characterized in that having the silicate-base composite material of multilayer classifying structure is undertaken by following step:
One, according to chemical formula Li 2MSiO 4, be that 2: 1: 1 ratio takes by weighing lithium salts, transition metal salt and tetraethoxysilane respectively according to Li element, M element and Si element mol ratio;
Two, at room temperature be dissolved in lithium salts, transition metal salt and carbonaceous organic material in the distilled water; Form solution 1; The mol ratio of carbonaceous organic material and lithium salts is 1: 0.05～5, and the mol ratio of lithium salts and transition metal salt is 2: 1, and the concentration of lithium salts is 0.01mol/L～5mol/L in the solution 1;
Three, put into agitated reactor after being dissolved in the distilled water according to 1: 0.01～4 mol ratio tetraethoxysilane and acetate; Then under 70 ℃, inert gas shielding; Carried out magnetic agitation 30 minutes with 100 rev/mins rotating speeds; Form solution 2, the concentration of tetraethoxysilane is 0.01mol/L～5mol/L in the solution 2;
Four, be that 1: 0.1～3 volume ratio is poured solution 1 in the solution 2 into according to solution 1 and solution 2; At the pressure of inert gas shielding, reaction system is that 0.02MPa～1MPa, temperature are under 60 ℃～120 ℃ the condition; Continuation was stirred 6 hours with 100 rev/mins rotating speed, formed colloidal sol 3;
Five, 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;
Six, with precursor powder sintering 8 hours under 600 ℃～900 ℃, hydrogen atmosphere, obtain black powder, promptly get silicate-base cell positive material with multilayer classifying structure; M in the step 1 is Mn, Fe, Co or Ni.
2. according to the said preparation method of claim 1, it is characterized in that lithium salts described in the step 1 is two water lithium acetates with silicate-base composite material of multilayer classifying structure.
3. according to claim 1 or 2 said preparation methods, it is characterized in that transition metal salt described in the step 1 is four water acetic acid manganese, Cobalt diacetate tetrahydrate, four water acetic acid nickel or five hydration ironic citrates with silicate-base composite material of multilayer classifying structure.
4. according to claim 1 or 2 said preparation methods, it is characterized in that carbonaceous organic material described in the step 2 is Citric Acid Mono, sucrose, glucose or starch with silicate-base composite material of multilayer classifying structure.
5. according to claim 1 or 2 said preparation methods, it is characterized in that inert gas described in the step 3 is nitrogen or argon gas with silicate-base composite material of multilayer classifying structure.
6. according to claim 1 or 2 said preparation methods, it is characterized in that inert gas described in the step 4 is nitrogen or argon gas with silicate-base composite material of multilayer classifying structure.
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Application publication date: 20120711