CN104167539A - A novel LiCo<1-x>Sn<x>O2 electrode material and a preparing method thereof - Google Patents

A novel LiCo<1-x>Sn<x>O2 electrode material and a preparing method thereof Download PDF

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Publication number
CN104167539A
CN104167539A CN201410316670.4A CN201410316670A CN104167539A CN 104167539 A CN104167539 A CN 104167539A CN 201410316670 A CN201410316670 A CN 201410316670A CN 104167539 A CN104167539 A CN 104167539A
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lico
solution
electrode material
precipitation
naoh
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不公告发明人
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A novel LiCo<1-x>Sn<x>O2 battery cathode material and a preparing method thereof are disclosed. According to the material and the method, LiNO3, Co(NO3)2, SnCl2 and NaOH are adopted as raw materials and a coprecipitation-method preparing process is adopted. The preparing method includes: dissolving the LiNO3, the Co(NO3)2 and the SnCl2 into an ethanol solution according to a ratio, dissolving the NaOH into another ethanol solution, adding the first mixture dropwise into the second mixture, mixing, filtering after reactions are completed to separate a precipitate, drying the separated precipitate in an environment having a temperature of 80 DEG C, drying, performing high-temperature calcination, and grinding to obtain a final product. The material and the preparing method have advantages of accurately controlled quantity relative ratio, high product purity, low calcination temperature, uniform synthesized product components, easily controlled conditions, simple operation, and the like.

Description

A kind of novel LiCo 1-xsn xo 2electrode material and preparation method thereof
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, particularly a kind of stratiform ternary transition metal oxide combination electrode material and preparation method thereof.
Background technology
At occurring in nature, elemental lithium is the lightest metal, and its atomic weight is 6.94g/mol, ρ=0.53g/cm 3, electrochemical equivalent is minimum, is 0.26 gAh -1standard electrode potential is the most negative, for-3.045 V, these features of elemental lithium have determined that it is a kind of very material of high-energy-density that has, lithium ion battery is exactly this characteristic of utilizing elemental lithium, lithium ion battery is a kind of rechargeable battery, mainly relies on lithium ion between positive pole and negative pole, to move work.In charge and discharge process, Li +between two electrodes, come and go and embed and de-embedding, during rechargable battery, Li +from the de-embedding of positive pole, through electrolyte, embed negative pole, negative pole is in rich lithium state; Contrary during electric discharge.Lithium ion battery gains great popularity because of advantages such as its voltage are high, energy density is high, have extended cycle life, environmental pollution is little, but along with the fast development of electronic information technology, the performance of lithium ion battery is also had higher requirement.
The selection of material is the first element that affects performance of lithium ion battery.From material angle, the cycle performance factor of material further develops restriction lithium battery, in the cyclic process of battery, thereby may be on the one hand that changes in crystal structure is too fast in cyclic process, cannot continue the de-lithium of embedding lithium, may be to cause active material and electrolyte that side reaction occurs too early to make the too fast consumption of electrolyte and then affect to circulate because active material and corresponding electrolyte cannot generate fine and close SEI film uniformly on the one hand.Therefore developing high performance electrode material is the key that improves battery performance.
Common anode material for lithium-ion batteries mainly contains cobalt acid lithium, the LiMn2O4 of spinel structure and the LiFePO4 of olivine structural of layer structure at present.Business-like lithium ion battery mainly adopts LiCoO 2as positive electrode, LiCoO 2there is fail safe and overcharge resistance performance problem, Co belongs to scarce resource, expensive, and metallic cobalt is easily to environment, its development space is restricted, reduced to a great extent the scope of application of boring series lithium ion battery, therefore fully utilize the good features such as cycle performance of cobalt acid lithium, fully by molecular level mix, the synthetic collaborative composite lithium-inserting oxide of multielement of method such as doping, coated and finishing, can reduce the content of electrode material Co, and employing doped with metal elements, can be to LiCoO 2lattice structure play certain support and stabilization, effectively suppress the phase transformation of cell configuration in charge and discharge process and subside, to reach the object of the safety, cycle performance and the discharge platform that improve material, the LiCo of the Sn that therefore adulterates 1-xsn xo 2electrode material has better development prospect.
Summary of the invention
The object of this invention is to provide a kind of anode material for lithium-ion batteries and preparation method thereof.
For realizing this purpose, the present invention is achieved through the following technical solutions:
Adopt the LiCo of the standby doping of coprecipitation legal system Sn 1-xsn xo 2electrode material.
The LiCo of a kind of Sn that adulterates 1-xsn xo 2electrode material preparation method, comprises the steps:
(1) with LiNO 3, Co (NO 3) 2and SnCl 2for raw material is by 1:(1-x): the mol ratio of x is dissolved in ethanolic solution, does not stop to shake up;
(2) get appropriate NaOH pressed powder and be dissolved in another part of ethanolic solution, do not stop to shake up;
(3) in the NaOH ethanolic solution in (2) the solution of joining in being (1) added drop-wise to the speed of 1 drop/sec, and constantly stir and react fully;
(4) in (3), solution, not when producing precipitation, stops splashing into;
(5) static a period of time, the solution in (4) by filtering to isolate precipitation;
(6) in will be (5), isolated precipitation be spread out and at 80 ℃ of dry 10h;
(7) drier postprecipitation in is (6) placed in to air 400-800 ℃ of calcining;
(8) gained solid abrasive after calcining is obtained to final products.
The present invention has following advantages and characteristic;
(1) amount is than can accurately controlling, and product purity is high;
(2) gained presoma particle diameter is little, and mixes;
(3) calcining heat is lower, and synthetic product component is even;
(4) favorable reproducibility, condition is easily controlled, simple to operate.
Embodiment
Embodiment mono-:
Get respectively a certain amount of LiNO 3, Co (NO 3) 2and SnCl 2powder, is dissolved in ethanolic solution by the mol ratio of 1:0.3:0.7, is mixed with the solution that metal ion concentration is 3mol/L; Separately getting appropriate NaOH pressed powder is dissolved in another part of ethanolic solution, be made into the NaOH ethanolic solution of 3mol/L, joined solion, the speed with 1 drop/sec is added drop-wise in NaOH ethanolic solution again, and constantly stirs and react fully, and mixing speed is 60r/min; Until solution, not when producing precipitation, stop splashing into and static a period of time, solution filter is isolated to precipitation, isolated precipitation is spread out and at 80 ℃ of dry 10h, after being dried, is placed in air 400 ℃ of calcinings again; Gained solid abrasive after calcining is obtained to final products.
Embodiment bis-:
Get respectively a certain amount of LiNO 3, Co (NO 3) 2and SnCl 2powder, is dissolved in ethanolic solution by the mol ratio of 1:0.5:0.5, is mixed with the solution that metal ion concentration is 3mol/L; Separately getting appropriate NaOH pressed powder is dissolved in another part of ethanolic solution, be made into the NaOH ethanolic solution of 3mol/L, joined solion, the speed with 1 drop/sec is added drop-wise in NaOH ethanolic solution again, and constantly stirs and react fully, and mixing speed is 80r/min; Until solution, not when producing precipitation, stop splashing into and static a period of time, solution filter is isolated to precipitation, isolated precipitation is spread out and at 80 ℃ of dry 10h, after being dried, is placed in air 600 ℃ of calcinings again; Gained solid abrasive after calcining is obtained to final products.
Embodiment tri-:
Get respectively a certain amount of LiNO 3, Co (NO 3) 2and SnCl 2powder, is dissolved in ethanolic solution by the mol ratio of 1:0.7:0.3, is mixed with the solution that metal ion concentration is 3mol/L; Separately getting appropriate NaOH pressed powder is dissolved in another part of ethanolic solution, be made into the NaOH ethanolic solution of 3mol/L, joined solion, the speed with 1 drop/sec is added drop-wise in NaOH ethanolic solution again, and constantly stirs and react fully, and mixing speed is 100r/min; Until solution, not when producing precipitation, stop splashing into and static a period of time, solution filter is isolated to precipitation, isolated precipitation is spread out and at 80 ℃ of dry 10h, after being dried, is placed in air 800 ℃ of calcinings again; Gained solid abrasive after calcining is obtained to final products.

Claims (4)

1. a LiCo 1-xsn xo 2the preparation method of electrode material, is characterized in that, this preparation method carries out according to the following steps:
(1) with LiNO 3, Co (NO 3) 2and SnCl 2for raw material is by 1:(1-x): the mol ratio of x is dissolved in ethanolic solution, does not stop to shake up;
(2) get appropriate NaOH pressed powder and be dissolved in another part of ethanolic solution, do not stop to shake up;
(3) in the NaOH ethanolic solution in (2) the solution of joining in being (1) added drop-wise to the speed of 1 drop/sec, and constantly stir and react fully;
(4) in (3), solution, not when producing precipitation, stops splashing into;
(5) static a period of time, the solution in (4) by filtering to isolate precipitation;
(6) in inciting somebody to action (5), isolated precipitation is spread out at 80 ℃ of dry 10h;
(7) more dried precipitation in being (6) placed in to air calcines;
(8) gained solid abrasive after calcining is obtained to final products.
2. a kind of LiCo according to claim 1 1-xsnr xo 2electrode material preparation method, is characterized in that, the X value scope in step in is (1) 0.3≤X≤0.7.
3. a kind of LiCo according to claim 1 1-xsn xo 2electrode material preparation method, is characterized in that, step (3) in the agitating mode that adopts be mechanical agitation, mixing speed is 60-100 r/min.
4. a kind of LiCo according to claim 1 1-xsn xo 2electrode material preparation method, is characterized in that, step (7) in institute's calcining heat be controlled within the scope of 400-800 ℃.
CN201410316670.4A 2014-07-06 2014-07-06 A novel LiCo<1-x>Sn<x>O2 electrode material and a preparing method thereof Pending CN104167539A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417874A (en) * 2002-11-28 2003-05-14 清华大学 Prepn of high-rate lithium ion battery cathode material

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1417874A (en) * 2002-11-28 2003-05-14 清华大学 Prepn of high-rate lithium ion battery cathode material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
S. VALANARASU ET.AL: "Synthesis and improved electrochemical performance of LiCo1-xSnxO2(x=0 to 0.1) powders", 《CRYST. RES. TECHNOL.》, vol. 45, no. 8, 11 June 2010 (2010-06-11), pages 835 - 839 *

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