CN103956456A - Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material - Google Patents

Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material Download PDF

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CN103956456A
CN103956456A CN201410160158.5A CN201410160158A CN103956456A CN 103956456 A CN103956456 A CN 103956456A CN 201410160158 A CN201410160158 A CN 201410160158A CN 103956456 A CN103956456 A CN 103956456A
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lithium
positive electrode
electrode material
rich
halide anion
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高学平
张洪周
李国然
叶世海
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Nankai University
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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
    • H01M4/50—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
    • 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
    • H01M4/48—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
    • H01M4/52—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
    • 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)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention relates to a halogen anion doped lithium-rich positive electrode material of a secondary battery as well as a preparation method and an application of positive electrode material. The expression formula of the halogen anion doped lithium-rich positive electrode material is Li[Li(1-2x)/3MxMn(2-x)/3]O2-zAz, wherein M is at least one or a combination of Co, Ni, Al, Mg, Zn, Ga, B, Zr, Ti, Ca, Ce, Y and Nb, A is at least one or a combination of Cl, Br or I, x is greater than 0 and less than 0.5, and z is greater than 0 and less than or equal to 0.5; when M is one or the combination of Ni and Co and A is Cl, x is not equal to 0.2. The preparation method comprises the following preparation steps: in the process of preparing a lamellar lithium-rich oxide positive electrode material Li[Li(1-2x)/3MxMn(2-x)/3]O2, introducing halogen anions A according to the stoichiometric ratio to prepare a solution, and then carrying out solidification, drying and calcination, thereby obtaining the halogen anion doped lithium-rich positive electrode material. If the halogen anion doped lithium-rich positive electrode material is used as the positive electrode material for a lithium battery, the first charge-discharge efficiency of the material can be improved; the structural transformation of the material in electrochemical cycle is inhibited. The electrochemical properties of the lithium-rich lamellar oxide positive electrode material are improved, and the lithium-rich lamellar oxide positive electrode material has the characteristics of high first charge-discharge efficiency, high capacity, good cycle performance, simple preparation process, good reproducibility and the like.

Description

Lithium-rich anode material of halide anion doping and its preparation method and application
Technical field
The present invention relates to the lithium-rich anode material and its preparation method and application of a kind of halide anion doping of secondary cell.
Background technology
Due to scientific and technological development, people are more and more higher to the requirement of energy storage.Lithium ion battery is because to have energy density high, and the advantage such as environmental protection and long service life relatively becomes the focus of research.As lithium ion battery key component, positive electrode plays an important role.The rich oxidate for lithium positive electrode of stratiform Li[Li (1-2x)/3m xmn (2-x)/3] O 2because there is the height ratio capacity over 200mAh/g, become the most possible positive electrode of lithium ion battery of future generation.Yet, the current rich oxidate for lithium positive electrode of the stratiform part that also comes with some shortcomings, mainly contain: first charge-discharge efficiency irreversible capacity loss first low and that cause is large, cyclic process laminate structure easily changes to spinel structure, voltage platform reduces, and then causes degradation problem under energy density.
In order to improve the problem of these aspects, according to existing bibliographical information, the method that the rich oxidate for lithium positive electrode of stratiform is carried out to modification mainly comprises that surface is coated, other pretreatment modes and body phase ion doping.Chinese patent CN200980150179.6 and CN201110434564.2 report, adopt the coated lithium-rich anode material of metal fluoride can improve its chemical property.CN201110111035.9 adopts the oxidants such as persulfate or sulfate to carry out surface preparation to material, and the efficiency first of material and powerful discharge capacity are improved.Aspect bulk phase-doped, current report mainly concentrates on metal cation doping, for example: CN200910186311.0 has reported that the method by cation doping improves the cycle performance of material and the method for high rate performance; CN201210391471.0 and CN201210391672.0 have reported respectively a kind of preparation method who adopts the rich lithium solid solution cathode material of doping trivalent ion and iron copper tin ion.Aspect anion doped, CN201310087241 has reported a kind of PO of using 4 3-, SO 4 2-, A1O 2 -the method of material being carried out to modification Deng polyanion doping; CN200980138690.4 adopts the performance of fluorine doping improved materials.CN201210216042.X adopts the method for doping chloride ion, but its material of stating can only contain Li, Ni, Co, Mn, O and Cl element in expression formula, and the content of Li is fixed to Li1.2.
Summary of the invention
Rich oxidate for lithium positive electrode of stratiform providing a kind of halide anion doping and preparation method thereof is provided the object of the invention, to improve the existing deficiency of rich lithium material, the advantages such as the present invention has that preparation method is simple, electrode material specific capacity is high, multiplying power and good cycle.
The expression formula of the rich oxidate for lithium positive electrode of a kind of halide anion doping stratiform provided by the invention is: Li[Li (1-2x)/3m xmn (2-x)/3] O 2-za z, M is at least one or its combination in Co, Ni, Al, Mg, Zn, Ga, B, Zr, Ti, Ca, Ce, Y, Nb element, a kind of or its combination in A=Cl, Br or I, 0 < x < 0.5; 0 < z≤0.5; Work as M=Ni, during a kind of or its combination and A=Cl in Co, x ≠ 0.2.
Preparation process is at the rich oxidate for lithium positive electrode of preparation stratiform Li[Li (1-2x)/3m xmn (2-x)/3] O 2process in, according to stoichiometric proportion, introduce halide anion A, be mixed with solution, through overcuring, dry, roasting, make Li[Li (1-2x)/3m xmn (2-x)/3] O 2-za z.
Described lithium-rich anode material is Li[Li 0.17ni 0.25mn 0.58] O 2, Li[Li 0.20ni 0.1al 0.03co 0.13mn 0.54] O 2or Li[Li 02co 0.4mn 0.4] O 2.
The lithium-rich anode material of described halide anion doping is Li[Li 017ni 0.25mn 058] O 1.85cl 0.15, Li[Li 0.22ni 0.05al 0.02co 0.1mn 0.61] O 194br 0.06or Li[Li 0.2co 0.4mn 0.4] O 1.98i 0.02.
The preparation method of the lithium-rich anode material of halide anion doping provided by the invention is through following step:
1) by metering than by lithium salts (lithium acetate or lithium nitrate or lithium hydroxide), nickel, manganese or (with) salt of cobalt salt (nitrate or acetate) and halide anion A (ammonium salt or manganese salt or with the salt of metal M formation) is mixed with the aqueous solution, wherein the quality of lithium salts is than stoichiometric proportion excessive 3～8%; Metal ion total concentration is 0.5～2 mole every liter; Then add citric acid, citric acid and total metal ion mol ratio are 2: 1, with ammoniacal liquor, the pH of mixed liquor are adjusted to 9, stir;
2) by step 1) prepared solution in spray dryer, spray dry, the precursor that obtains mixing;
3) by step 2) the presoma product of gained is transferred in crucible, and under 420～500 ℃ of conditions, roasting is 4～9 hours;
4) by step 3) products therefrom grinding, under 700～900 ℃ of conditions, roasting is 10～22 hours, obtains product Li[Li (1-2x)/3m xmn (2-x)/3] O 2-za z.
The salt that described halide anion source is M element in the ammonium salt, manganese salt or the expression formula that contain this halide anion.
Described nickel, cobalt salt and manganese salt are respectively their nitrate or acetate.
The layered oxide positive electrode Li[Li that the present invention obtains (1-2x)/3m xmn (2-x)/3] O 2-za zcan be directly used in manufacture lithium ion battery.
Advantage of the present invention is, the layered oxide Li[Li of halide anion doping (1-2x)/3m xmn (2-x)/3] O 2-za zmaterial is during as anode material for lithium-ion batteries 1) can suppress the oxygen of material in initial charge process and separate out, thus can improve the first charge-discharge efficiency of material; 2) halide anion of doping has been stablized the structure of material, has suppressed the Structure Transformation of material in electrochemistry circulation; 3) halide anion is entrained in the decline that has delayed to a certain extent voltage platform.Therefore the present invention has improved the chemical property of rich lithium layered oxide positive electrode, has first charge-discharge efficiency high, and capacity is high, good cycle, the features such as the simple favorable reproducibility of preparation process.
Accompanying drawing explanation
Fig. 1 is the prepared Li[Li of embodiment 1 0.17ni 025mn 0.58] O 1.85cl 0.15the X-ray diffraction of positive electrode (XRD) figure.
Fig. 2 is the prepared Li[Li of embodiment 1 0.17ni 0.25mn 0.58] O 185cl 0.15the transmission electron microscope of positive electrode (TEM) photo.
Fig. 3 is the prepared Li[Li of embodiment 1 017ni 0.25mn 0.58] O 1.85cl 0.15the discharge curve of positive electrode under 30 milliamperes of every gram of current densities.
Fig. 4 is the prepared Li[Li of embodiment 2 0.22ni 005al 0.02co 0.1mn 0.61] O 1.94br 0.06the discharge capacity cyclic curve of positive electrode under 30 milliamperes of every gram of current densities.
Fig. 5 is the prepared Li[Li of embodiment 3 0.2co 0.4mn 04] O 1.98i 002the discharge curve of positive electrode under 30 milliamperes of every gram of current densities.
Embodiment
The present invention can be embodied from following embodiment, but just presented for purposes of illustration, rather than for limiting the present invention.
Embodiment 1
Li[Li 017ni 0.25mn 058] O 1.85cl 0.15preparation:
Take 6.248 grams of CH 3cOOLi2H 2o, 3.111 grams of Ni (CH 3cOO) 22H 2o, 6.229 grams of Mn (CH 3cOO) 22H 2o and 0.7422 gram of MnCl 24H 2o, is mixed with 200 ml water solution, then adds the citric acid of 200 milliliters 1.0 moles every liter, adds ammoniacal liquor that the pH of mixed liquor is adjusted to 9, stirs; Above-mentioned solution is injected into spray dryer, and (Beijing Lai Heng science and trade Co., Ltd, sprays in L-217) dry, the precursor that obtains mixing; By gained precursor grind into powder, be transferred in crucible, at 480 ℃, roasting is 7.5 hours, cooling after, material is ground and ground material is placed in to 900 ℃ of high temperature sinterings of Muffle furnace 10 hours, finally make the Li[Li of halide anion doping 017ni 0.25mn 0.58] O 1.85cl 0.15material.Fig. 1 is X-ray diffraction (XRD) figure of prepared material, does not occur the diffraction maximum of other compounds in figure, and the body phase crystal structure of testimonial material is not because doped with Cl -and change.Fig. 2 is transmission electron microscope (TEM) figure of prepared material, and as can be seen from the figure material granule is that class is spherical, and particle diameter is in 100-200 nanometer range.
Electrochemical property test is as follows: the rich lithium material that the prepared halide anion of take adulterates is positive electrode, take lithium metal as to electrode, be assembled into according to a conventional method half-cell, assembled battery is carried out to constant current charge-discharge test at ambient temperature, voltage range is: 2.0～4.8 volts.Fig. 3 has shown under 30 milliamperes of every gram of current densities, the discharge curve of material.As can be seen from Figure 3, prepared material discharging capacity is 275.1mAh/g, has higher specific discharge capacity.
Embodiment 2
Li[Li 022ni 0.05al 0.02co 0.1mn 0.61] O 1.94br 0.06preparation:
By the CH in embodiment 1 3cOOLi2H 2o quality changes 6.5456 grams into, Ni (CH 3cOO) 22H 2o quality changes 0.5807 gram into, Mn (CH 3cOO) 22H 2o quality changes 7.4889 grams into.Add Co (CH 3cOO) 22H 2o quality is 1.2454g, NH 4br quality is 0.2938g, Al (NO 3) 39H 2o quality is 0.3751g.Other can make Li[Li with embodiment 1 022ni 0.05al 0.02co 0.1mn 061] O 1.94br 0.06material.Fig. 4 has shown its chemical property, under 30 milliamperes of every gram of current densities, mixes the Li[Li of Br ion 0.22ni 0.05al 0.02co 0.1mn 0.61] O 1.94br 0.06the specific discharge capacity of material after 30 weeks is every gram of 223.0 MAH, and cycle performance is excellent.
Embodiment 3
Li[Li 0.2co 0.4mn 0.4] O 1.98i 0.02the preparation of material:
Ni (CH will be removed in embodiment 1 3cOO) 22H 2o, MnCl 24H 2o.Mn (CH 3cOO) 22H 2o quality changes 4.902 grams into, adds Co (CH 3cOO) 22H 2o quality is 4.9816g, and LiI quality is 0.1879g.CH 3cOOLi2H 2o quality changes 6.3246g into, and other can make Li[Li with embodiment 1 0.2co 0.4mn 04] O 1.98i 0.02material.Figure 5 shows that under 30 milliamperes of every gram of current densities, the head of the material that this example is prepared week charging and discharging curve, adulterates after I as seen from the figure, and material has higher specific discharge capacity equally.

Claims (8)

1. a lithium-rich anode material for halide anion doping, is characterized in that it forms expression formula and is: Li[Li (1-2x)/3m xmn (2-x)/3] O 2-za z, M is at least one or its combination in Co, Ni, Al, Mg, Zn, Ga, B, Zr, Ti, Ca, Ce, Y, Nb element, a kind of or its combination in A=Cl, Br or I, 0 < x < 0.5; 0 < z≤0.5; Work as M=Ni, during a kind of or its combination and A=Cl in Co, x ≠ 0.2.
2. the lithium-rich anode material of halide anion doping according to claim 1, is characterized in that M is a kind of or its combination in Co, Ni, Al, Mg, Zn, Ga, B, Zr, Ti, Ca, Ce, Y, Nb element.
3. the lithium-rich anode material of halide anion doping according to claim 1, is characterized in that described lithium-rich anode material is Li[Li 017ni 0.25mn 058] O 2, Li[Li 0.20ni 0.1al 0.03co 0.13mn 0.54] O 2or Li[Li 0.2co 0.4mn 0.4] O 2.
4. the lithium-rich anode material of halide anion doping according to claim 1, is characterized in that it is Li[Li 0.17ni 0.25mn 0.58] O 1.85cl 015li[Li 022ni 0.05al 002co 0.1mn 061] O 1.94br 006or Li[Li 0.2co 04mn 0.4] O 1.98i 002.
5. the preparation method of the lithium-rich anode material that halide anion claimed in claim 1 adulterates, is characterized in that it is through following step:
1) by metering than by lithium salts or lithium hydroxide, nickel, manganese or \ be mixed with the aqueous solution with the salt of cobalt salt and halide anion A, wherein the quality of lithium salts is than stoichiometric proportion excessive 3～8%; Metal ion total concentration is 0.5～2 mole every liter; Then add citric acid, citric acid and total metal ion mol ratio are 2: 1, with ammoniacal liquor, the pH of mixed liquor are adjusted to 9, stir;
2) by step 1) prepared solution in spray dryer, spray dry, the precursor that obtains mixing;
3) by step 2) the presoma product of gained is transferred in crucible, and under 420～500 ℃ of conditions, roasting is 4～9 hours;
4) by step 3) products therefrom grinding, under 700～900 ℃ of conditions, roasting is 10～22 hours, obtains product Li[Li (1-2x)/3m xmn (2-x)/3] O 2-za z.
6. preparation method according to claim 5, is characterized in that the salt that described halide anion source is M element in the ammonium salt, manganese salt or the expression formula that contain this halide anion.
7. preparation method according to claim 5, is characterized in that described nickel, cobalt salt and manganese salt are respectively their nitrate or acetate.
8. the arbitrary described lithium-rich anode material of claim 1-4 is for the manufacture of lithium ion battery.
CN201410160158.5A 2014-04-17 2014-04-17 Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material Pending CN103956456A (en)

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Cited By (7)

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CN104393280A (en) * 2014-11-19 2015-03-04 陈梅 Preparation method of manganese-cobalt-lithium positive pole material
WO2018215254A1 (en) * 2017-05-24 2018-11-29 Basf Se Process for making an electrode active material
CN109921016A (en) * 2019-03-11 2019-06-21 安徽师范大学 A kind of copper sulfide micron floral material and its preparation method and application that halide ion is assisted
CN111224090A (en) * 2020-03-12 2020-06-02 河南电池研究院有限公司 Composite lithium-rich manganese-based positive electrode material and preparation method thereof
CN112072114A (en) * 2020-09-17 2020-12-11 中南大学 Anion-cation co-doped lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN112652771A (en) * 2020-12-22 2021-04-13 北京理工大学重庆创新中心 Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof
WO2024131289A1 (en) * 2022-12-19 2024-06-27 上海交通大学 Layered positive electrode material for lithium-ion battery, and preparation method therefor and use thereof

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CN102723472A (en) * 2012-06-27 2012-10-10 江南大学 Chlorine-doped modified lithium ion battery lithium-rich cathode material and preparation method thereof
CN103199229A (en) * 2013-03-19 2013-07-10 南开大学 Polyanion-doped lithium-enriched layered oxide anode material as well as preparation and application thereof
CN103441265A (en) * 2013-09-24 2013-12-11 上海空间电源研究所 Co-doped lithium-rich composite anode material and preparation method thereof

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WO2010039732A2 (en) * 2008-09-30 2010-04-08 Envia Systems, Inc. Fluorine doped lithium rich metal oxide positive electrode battery materials with high specific capacity and corresponding batteries
CN102723472A (en) * 2012-06-27 2012-10-10 江南大学 Chlorine-doped modified lithium ion battery lithium-rich cathode material and preparation method thereof
CN103199229A (en) * 2013-03-19 2013-07-10 南开大学 Polyanion-doped lithium-enriched layered oxide anode material as well as preparation and application thereof
CN103441265A (en) * 2013-09-24 2013-12-11 上海空间电源研究所 Co-doped lithium-rich composite anode material and preparation method thereof

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104393280A (en) * 2014-11-19 2015-03-04 陈梅 Preparation method of manganese-cobalt-lithium positive pole material
CN104393280B (en) * 2014-11-19 2017-12-15 广州盘太能源科技有限公司 A kind of preparation method of manganese cobalt lithium anode material
WO2018215254A1 (en) * 2017-05-24 2018-11-29 Basf Se Process for making an electrode active material
US11394026B2 (en) 2017-05-24 2022-07-19 Basf Se Process for making an electrode active material
CN109921016A (en) * 2019-03-11 2019-06-21 安徽师范大学 A kind of copper sulfide micron floral material and its preparation method and application that halide ion is assisted
CN111224090A (en) * 2020-03-12 2020-06-02 河南电池研究院有限公司 Composite lithium-rich manganese-based positive electrode material and preparation method thereof
CN111224090B (en) * 2020-03-12 2022-08-05 河南电池研究院有限公司 Composite lithium-rich manganese-based positive electrode material and preparation method thereof
CN112072114A (en) * 2020-09-17 2020-12-11 中南大学 Anion-cation co-doped lithium-rich manganese-based positive electrode material and preparation method and application thereof
CN112652771A (en) * 2020-12-22 2021-04-13 北京理工大学重庆创新中心 Polyanion-doped single-crystal high-nickel positive electrode material and preparation method thereof
WO2024131289A1 (en) * 2022-12-19 2024-06-27 上海交通大学 Layered positive electrode material for lithium-ion battery, and preparation method therefor and use thereof

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