CN1501529A - Positive electrode material of surface finishing modified lithium ion cell and method for making same - Google Patents

Positive electrode material of surface finishing modified lithium ion cell and method for making same Download PDF

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Publication number
CN1501529A
CN1501529A CNA021395586A CN02139558A CN1501529A CN 1501529 A CN1501529 A CN 1501529A CN A021395586 A CNA021395586 A CN A021395586A CN 02139558 A CN02139558 A CN 02139558A CN 1501529 A CN1501529 A CN 1501529A
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China
Prior art keywords
lithium
ion
lithium ion
positive pole
anode material
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CNA021395586A
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Chinese (zh)
Inventor
园 周
周园
马培华
贾永忠
韩金铎
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Qinghai Institute of Salt Lakes Research of CAS
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Qinghai Institute of Salt Lakes Research of CAS
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Priority to CNA021395586A priority Critical patent/CN1501529A/en
Publication of CN1501529A publication Critical patent/CN1501529A/en
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a surface finished Li-ion battery anode material and method for making same, wherein the anode material comprises a substrate and a surface modified layer, the method comprises proceeding surface finishing to the Li-ion battery anode material which is prepared in advance through homogeneous reaction with high crystal quality and uniform pore space, the Li-ion battery anode material made therefrom has good compatibility with electrolyte solution and the advantages of small specific surface area, apparent specific gravity and stable electrochemical property.

Description

Surface modified positive pole material of lithium ion cell and preparation method thereof
Technical field
The present invention relates to a kind of modification technology of anode material for lithium-ion batteries, especially a kind of lithium ion battery surface modification positive electrode and preparation method thereof with superior cycle life.
Background technology
Lithium ion battery is meant with different lithium intercalation compounds to be the secondary cell of both positive and negative polarity, general cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound of adopting is as positive pole, adopting lithium to insert carbon compound as negative pole, is that electrolyte is formed battery with the organic solution that is dissolved with lithium salts.In charge and discharge process, Li +Between the two poles of the earth, come and go embedding and take off discharging and recharging of embedding realization battery.Lithium ion battery operating voltage height, but energy density is big, security performance good, the little fast charging and discharging of self discharge, can make large-capacity battery pack, and is the memory-less effect battery.Along with modern electrical equipment microminiaturization, the needs of energetic, good power supply in light weight, that volume is little, high specific energy, high voltage, oligosaprobic lithium ion battery will become office, communication, computer, video camera and electric automobile etc.Because lithium ion battery excellent charging and discharging reversibility and fail safe have potential advantage competition power on Battery Market, make countries in the world all fall over each other developmental research.
Lithium ion battery popularize and application process in, the performance of battery and price are decisive factors, and superior, the low-cost lithium intercalation compound of processability be positive electrode is a key wherein.
The method of synthetic positive electrode has solid phase method and liquid phase method.High temperature solid-state is synthetic to be to carry out long-time in air raw materials such as carbonate, nitrate, acetate, oxide or the hydroxide mixing back of lithium, transition metal and the multistage heating.Low temperature solid phase synthesis rule is with raw material grinding for a long time in different atmosphere or organic solvent of lithium and transition metal, adds thermal bake-out in uniform temperature then.Also have fused salt infusion process, Pechini method, coprecipitation, low temperature semi-solid phase method etc. in addition.The positive electrode and the electrolyte solution compatibility of these different synthetic methods preparations are poor at present, and the two reacts and positive electrode is dissolved at material surface and causes the chemical property instability, makes the battery charging and discharging life-span shorten dramatically.
Summary of the invention
The objective of the invention is to adopt the preparation of surface modified technology can be good compatible, have the superior cycle life anode material for lithium-ion batteries with electrolyte solution in order to provide a kind of.
Another object of the present invention is for a kind of surface modified positive pole material of lithium ion cell preparation method is provided, the surface topography of this method may command material, improve the compatibility of positive electrode and electrolyte solution, stable electrical chemical property, the charge-discharge performance of raising positive electrode; The lithium ion battery charge-discharge performance that material of the present invention is made is stable, capacity is reliable.
Purpose of the present invention can realize by following measure:
A kind of surface modified positive pole material of lithium ion cell is made up of the modified layer on base material and the base material; Wherein the molecular structural formula of base material is LiM XN 1-XO 2Or LiM XMn 2-XO 4, molecular structural formula is LiM XN 1-XO 2Formula in M, N be selected from a kind of in Co, Ni, the Mn transition metal, x is 0≤x＜0.8; , molecular structural formula is LiM XMn 2-XM in the O formula be selected from Co, Ni, Cr any, X is 0≤X＜0.4; The molecular structural formula of modified layer is A xB yO z, wherein A, B are selected from any in Li, Mg, Al, Sn, the B element, and x is that 0≤x≤8, y are that 0＜x≤5, z are 0＜x≤10 in the formula.
Described modification ion is selected from Li +, Mg 2+, Al 3+, Sn 2+, BO 3 3-At least a in the ion, and the modification ion that is adsorbed on the positive electrode surface be in the positive electrode after the modification except that lithium ion the 0.005-0.05 of the total weight of all the other cations.
Described anode material for lithium-ion batteries is a kind of in cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound.
Another object of the present invention also can realize by following measure:
A kind of preparation method of surface modified positive pole material of lithium ion cell comprises the steps:
(1) with the positive electrode of lithium ion battery, 2-20% adds in the modified solution that molar concentration is 0.01-1mol/L and carries out adsorption reaction at anode material for lithium-ion batteries surface adsorption modification ion by weight percentage;
(2) the modification ion with the anode material for lithium-ion batteries surface adsorption carries out the surface modified positive pole material of lithium ion cell that roasting is converted into surperficial tool oxide.
Described modified solution is selected from and contains Li +, Mg 2+, Al 3+, Sn 2+, BO 3 3-In at least a solion.
The anode material for lithium-ion batteries that above-mentioned steps (2) 2～15 hour gets final product surface modifiedly at 200～900 ℃, roasting the anode material for lithium-ion batteries of surface adsorption modification ion.
Described anode material for lithium-ion batteries is a kind of in cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound.
The present invention has following advantage compared to existing technology:
1, the present invention adopts Li +, Mg 2+, Al 3+, Sn 2+, BO 3 3-Plasma is to cobalt acid lithium, lithium nickelate and the LiMn2O4 and the surface modified preparation anode active material of lithium ion battery of their modified compound of general employing, the surface topography of control material, improve the compatibility of positive electrode and electrolyte solution, the stable electrical chemical property, the charge-discharge performance of raising positive electrode.The lithium ion battery charge-discharge performance that material of the present invention is made is stable, capacity is reliable.
2, the present invention be advantageous in that method is simple, simple equipments, practicality, low energy consumption, be easy to realize large-scale industrial production.
Concrete execution mode
The present invention also can be described in further detail in conjunction with the embodiments:
Embodiment one:
A kind of preparation spinelle phase LiMn 2O 4The method of surface modified positive pole material of lithium ion cell: with spinelle phase LiMn 2O 4Grind screening, the material powder of getting the 5g particle diameter and be 25 μ m joins the Mg that 100mL concentration is 0.1mol/L (Ac) 2The aqueous solution, slowly even continuous stirring 2-5 hour, row left standstill 1-2 hour again.Above-mentioned mixed liquor is transferred in the 2# sand core funnel, and elimination solution eliminates at 60-120 ℃ of vacuum drying oven wet mash with moisture content.Material after the taking-up oven dry was in 350-750 ℃ of roasting 2-15 hour.Gained surface modified positive pole material of lithium ion cell LiMn 2O 4Mg/Mn+Mg is 0.008 in the product, and specific capacity is 105mAh/g, charges and discharge efficient during its charge and discharge cycles 50 times and still reaches 97.0%.
Embodiment two:
A kind of preparation spinelle phase LiCo 0.1Mn 1.9O 4The method of surface modified positive pole material of lithium ion cell: with spinelle phase LiCo 0.1Mn 1.9O 4Grind screening, the material powder of getting the 10g particle diameter and be 25 μ m joins the H that 100mL concentration is 0.5mol/L 3BO 3The aqueous solution, slowly even continuous stirring 2-5 hour, row left standstill 1-2 hour again.Above-mentioned mixed liquor is transferred in the 2# sand core funnel, and elimination solution eliminates at 60-120 ℃ of vacuum drying oven wet mash with moisture content.Material after the taking-up oven dry was in 220-650 ℃ of roasting 2-15 hour.Gained is H 3BO 3Surface modified anode material for lithium-ion batteries B/Mn+Co+B is 0.009, and specific capacity is 97mAh/g, charges and discharge efficient during its charge and discharge cycles 50 times and still reaches 98.0%.
Embodiment three:
A kind of preparation spinelle phase LiCo 0.1Mn 1.9O 4The method of surface modified positive pole material of lithium ion cell: with spinelle phase LiCo 0.1Mn 1.9O 4Grind screening, the material powder of getting the 8g particle diameter and be 10 μ m joins the LiOH aqueous solution that 100mL concentration is 1.0mol/L, and slowly evenly continuous stirring 2-5 hour, row left standstill 1-2 hour again.Above-mentioned mixed liquor is transferred in the 2# sand core funnel, and elimination solution eliminates at 60-120 ℃ of vacuum drying oven wet mash with moisture content.Material after the taking-up oven dry was in 300-680 ℃ of roasting 2-15 hour.Gained is H 3BO 3Surface modified anode material for lithium-ion batteries Li/Co+Li is 0.01, and specific capacity is 97mAh/g, charges and discharge efficient during its charge and discharge cycles 50 times and still reaches 98.0%.
Embodiment four:
A kind of preparation LiNi 0.8Co 0.2O 2The method of surface modified positive pole material of lithium ion cell: with LiNi 0.8Co 0.2O 2Grind screening, the material powder of getting the 6g particle diameter and be 10 μ m joins the Al (NO that 100mL concentration is 0.05mol/L 3) 39H 2The O aqueous solution, slowly even continuous stirring 2-5 hour, row left standstill 1-2 hour again.Above-mentioned mixed liquor is transferred in the 2# sand core funnel, and elimination solution eliminates at 60-120 ℃ of vacuum drying oven wet mash with moisture content.Material after the taking-up oven dry was in 200-540 ℃ of roasting 2-15 hour.Gained is Al 2O 3Surface modified anode material for lithium-ion batteries Al/Ni+Co+Al is 0.05, and specific capacity is 176mAh/g, charges and discharge efficient during its charge and discharge cycles 50 times and still reaches 98.0%.

Claims (7)

1, a kind of surface modified positive pole material of lithium ion cell is made up of the modified layer on base material and the base material; Wherein the molecular structural formula of base material is LiM XN 1-XO 2Or LiM XMn 2-XO 4, molecular structural formula is LiM XN 1-XO 2Formula in M, N be selected from a kind of in Co, Ni, the Mn transition metal, x is 0≤x＜0.8; , molecular structural formula is LiM XMn 2-XM in the O formula be selected from Co, Ni, Cr any, X is 0≤X＜0.4; The molecular structural formula of modified layer is A xB yO z, wherein A, B are selected from any in Li, Mg, Al, Sn, the B element, and x is that 0≤x≤8, y are that 0＜x≤5, z are 0＜x≤10 in the formula.
2, surface modified positive pole material of lithium ion cell as claimed in claim 1 is characterized in that described modification ion is selected from Li +, Mg 2+, Al 3+, Sn 2+, BO 3 3-At least a in the ion, and the modification ion that is adsorbed on the positive electrode surface be in the positive electrode after the modification except that lithium ion the 0.005-0.05 of the total weight of all the other cations.
3, surface modified positive pole material of lithium ion cell as claimed in claim 1 is characterized in that described anode material for lithium-ion batteries is a kind of in cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound.
4, the preparation method of the described surface modified positive pole material of lithium ion cell of a kind of claim 1 comprises the steps:
(1) with the positive electrode of lithium ion battery, 2-20% adds in the modified solution that molar concentration is 0.01-1mol/L and carries out adsorption reaction at anode material for lithium-ion batteries surface adsorption modification ion by weight percentage;
(2) the modification ion with the anode material for lithium-ion batteries surface adsorption carries out the surface modified positive pole material of lithium ion cell that roasting is converted into surperficial tool oxide.
5, the preparation method of surface modified positive pole material of lithium ion cell as claimed in claim 4, it is characterized in that described modified solution is selected from contains Li +, Mg 2+, Al 3+, Sn 2+, BO 3 3-In at least a solion.
6, the preparation method of surface modified positive pole material of lithium ion cell as claimed in claim 4 is characterized in that the anode material for lithium-ion batteries that above-mentioned steps (2) 2～15 hour gets final product surface modifiedly at 200～900 ℃, roasting the anode material for lithium-ion batteries of surface adsorption modification ion.
7, the preparation method of surface modified positive pole material of lithium ion cell as claimed in claim 4 is characterized in that described anode material for lithium-ion batteries is a kind of in cobalt acid lithium, lithium nickelate and LiMn2O4 and their modified compound.
CNA021395586A 2002-11-16 2002-11-16 Positive electrode material of surface finishing modified lithium ion cell and method for making same Pending CN1501529A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100413122C (en) * 2004-11-03 2008-08-20 深圳市比克电池有限公司 Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method
CN110756211A (en) * 2019-09-29 2020-02-07 北京石墨烯技术研究院有限公司 Oxygen electrode catalyst and preparation method and application thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100413122C (en) * 2004-11-03 2008-08-20 深圳市比克电池有限公司 Manganese-included multi-element metal oxide, lithium ion secondary battery anode material and its preparing method
CN110756211A (en) * 2019-09-29 2020-02-07 北京石墨烯技术研究院有限公司 Oxygen electrode catalyst and preparation method and application thereof
CN110756211B (en) * 2019-09-29 2020-08-25 北京石墨烯技术研究院有限公司 Oxygen electrode catalyst and preparation method and application thereof

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