CN105304905A - Modified material for positive electrode of lithium ion battery and preparation method of modified material - Google Patents

Modified material for positive electrode of lithium ion battery and preparation method of modified material Download PDF

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Publication number
CN105304905A
CN105304905A CN201510611935.8A CN201510611935A CN105304905A CN 105304905 A CN105304905 A CN 105304905A CN 201510611935 A CN201510611935 A CN 201510611935A CN 105304905 A CN105304905 A CN 105304905A
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China
Prior art keywords
lithium
positive electrode
lithium ion
positive
ion battery
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CN201510611935.8A
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Chinese (zh)
Inventor
樊少娟
汪涛
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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Priority to CN201510611935.8A priority Critical patent/CN105304905A/en
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/62Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624Electric conductive fillers
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention relates to a modified material for a positive electrode of a lithium ion battery and a preparation method of the modified material. The method is characterized in that a Cu<2-x>Se(0.15<=x<=0.25) material coats the surface of a positive electrode material, or the positive electrode material is subjected to phase doping modification; the positive electrode material is one or the mixture of several from lithium cobalt oxides, nickel and cobalt lithium manganate, lithium nickel cobaltate, lithium iron phosphate, lithium iron/manganese phosphate, lithium manganate, lithium nickel cobaltate or lithium nickel manganese oxides. The mol ratio of the Cu<2-x>Se(0.15<=x<=0.25) material to the positive material is (0.001 to 0.2):1. When the modified material prepared by the method is used for the positive electrode of the lithium ion battery, the electric conductivity is improved; the lithium-ion transmission is facilitated; meanwhile, the goal of inhibiting the contact of the positive electrode and electrolyte can also be achieved; the first-time efficiency, the rate performance and the stability of the lithium ion battery are improved; the cycle life of the lithium ion battery is prolonged.

Description

A kind of material modified and preparation method thereof for lithium ion cell positive
Technical field
The present invention relates to field of lithium ion battery anode, be specifically related to Cu 2-xse (0.15≤x≤0.25) material is to the method for modifying of anode material for lithium-ion batteries and battery performance.
Background technology
Advantages such as operating voltage is high owing to having for lithium ion battery, energy density is large, have extended cycle life, security performance is good, pollution-free and be widely used and pay close attention to.Along with going deep into of research, have higher requirement to aspects such as the energy density of lithium ion battery, cycle performance and security performances, wherein positive electrode is a principal element of these aspects of limiting lithium ion cell development.
The chemical property being applied to the cobalt acid lithium material of suitability for industrialized production is the earliest more stable, and electric conductivity is better, good cycle, and especially compacted density can reach 4.0g/cm3, but its over-charge safety performance is poor.Although LiMn2O4 has higher specific capacity, but structural stability is poor, nickel doping LiMn2O4 because of the energy density that there is higher voltage platform corresponding higher, but the cycle performance under high temperature is poor, ternary material has Heat stability is good, energy density advantages of higher, but the aspects such as cycle performance, compacted density, security performance are poor.
In order to improve positive electrode, conventional method be positive pole material surface is adulterated, surface coating modification.Cu 2-xse (0.15≤x≤0.25) is a kind of material of face-centred cubic structure, has good chemical property.
Summary of the invention
The object of the invention is to, a kind of material modified and preparation method thereof for lithium ion cell positive is provided.The method adopts Cu 2-xse (0.15≤x≤0.25) carries out modification to lithium ion anode material, effectively can improve the electric conductivity of positive electrode, high rate performance and cycle performance.
Object of the present invention can be achieved through the following technical solutions:
A kind of material modified and preparation method thereof for lithium ion cell positive, described lithium ion battery comprises: positive plate, negative plate, be interval in barrier film between adjacent positive/negative plate and electrolyte; Described positive plate utilizes Cu 2-xse Material coating, wherein 0.15≤x≤0.25, carry out the modification of anode material for lithium-ion batteries.
Described material modified and preparation method thereof for lithium ion cell positive, realizes by one or more common implementings in following method:
(1) by Cu 2-xse (0.15≤x≤0.25) material is coated on positive electrode surface;
(2) by Cu 2-xse (0.15≤x≤0.25) material carries out bulk phase-doped modified to positive electrode;
(3) by Cu 2-xse (0.15≤x≤0.25) material carries out bulk phase-doped modified to positive electrode and is coated on positive electrode surface simultaneously;
(4) by Cu 2-xse (0.15≤x≤0.25) material and anode material for lithium-ion batteries are according to stoichiometric proportion, and after adopting solid phase method or liquid phase method to make the two mix, in atmosphere furnace, namely high temperature solid-phase sintering obtains the lithium ion battery composite cathode material of modification;
(5) by Cu 2-xse (0.15≤x≤0.25) and the raw material preparing positive electrode mix according to stoichiometric proportion to be prepared, namely obtain the lithium ion battery composite cathode material of modification through high temperature solid-phase sintering.
Preferably, described anode material for lithium-ion batteries is one or more mixing in cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickel cobalt dioxide or nickel ion doped; Described Cu 2-xthe mol ratio of Se (0.15≤x≤0.25) material and positive electrode is 0.001-0.2:1.
Beneficial effect of the present invention: (1) Cu 2-xse (0.15≤x≤0.25) is fast-ionic conductor at normal temperatures, the wherein Se atomic building braced frame of face-centred cubic structure, Cu atom then lack of alignment, Cu room intrinsic in this kind of structure constitutes the passage that ion can move, and under normal temperature, the ionic conductivity of this kind of material is 1.5 × 10 -2Ω -1cm -1, this kind of material is good p-type semiconductor in addition, and conductivity is 10 4-10 5Ω -1cm -1between, thus the conductivity of material can be improved, improve efficiency first and the high rate performance of battery.
(2) this kind of material is utilized to carry out surface modification to positive electrode, coating layer is made while isolated electrolyte and positive electrode, lithium ion freely to be passed through, thus while completing discharge and recharge, avoid electrolyte decomposition under high voltages, improve cycle life and the stability of ion battery.
(3) material price that the present invention is used is cheap, simple to operate, and technique is easy to control.
Accompanying drawing explanation
Fig. 1 is the anode material for lithium-ion batteries first charge-discharge curve chart of the modification of embodiment 1;
Fig. 2 is the anode material for lithium-ion batteries of the modification of embodiment 1 and unmodified cycle charge-discharge curve chart;
Fig. 3 is the anode material for lithium-ion batteries of the modification of embodiment 1 and unmodified discharge curve under different multiplying.
Embodiment
In order to have darker understanding to the present invention; below in conjunction with embodiment, technical scheme is clearly and completely described; but the embodiment of this aspect is only used to explain the present invention; and unrestricted the present invention; the every other case study on implementation that those skilled in the art obtain under whether making the prerequisite of creative work, all belongs to protection scope of the present invention.
Embodiment 1:
LiNi is pressed for raw material with lithium carbonate, nickel protoxide, mangano-manganic oxide 0.5mn 1.5o 4prepare burden, after mixing, 900 DEG C of constant temperature 18h in atmosphere, and carry out 700 DEG C of annealing 24h.With LiNi 0.5mn 1.5o 4matrix, Cu 1.78se is coated on blapharoplast surface, wherein LiNi 0.5mn 1.5o 4and Cu 1.78the mol ratio of Se is 1:0.05.
The electrochemical property test of material adopts blue electric battery test system at room temperature to test.Cycle performance test condition: test voltage scope be 3V-4.9V, 0.2C discharge and recharge once, 0.2C charge, 0.5C/1C/5C/10C respectively discharges once; High rate performance test condition: test voltage scope is 3V-4.9V, carries out discharge and recharge with 1C multiplying power, circulates 200 weeks, examination capability retention.The specific discharge capacity of material under 0.2C multiplying power is 126.4mAh/g, specific discharge capacity under 0.5C multiplying power is 124.5mAh/g, specific discharge capacity under 1C multiplying power is 122.6mAh/g, specific discharge capacity under 2C multiplying power is 121.7mAh/g, specific discharge capacity under 3C multiplying power is 120.5mAh/g, specific discharge capacity under 4C multiplying power is 119mAh/g, and it is better that high rate performance compares unmodified material.1C discharge cycles 200 weeks capability retentions are greater than 94%, and cycle performance is better.
Embodiment 2:
With lithium carbonate, manganese dioxide, 1% Cu 1.8se is raw material, is LiMn by the lithium ion battery composite cathode material composition of gained modification 2o 4.0.01Cu 1.8the stoichiometric proportion of Se is prepared burden, after mixing, and 1000 DEG C of constant temperature 24h in air atmosphere, and carry out annealing 700 DEG C of 24h, obtain Cu 1.8the bulk phase-doped LiMn of Se 2o 4composite positive pole.
Embodiment 3:
With lithium carbonate, ferrous oxalate, ammonium dihydrogen phosphate, 1% Cu 1.85for raw material, by the lithium ion battery composite cathode material composition LiFePO of gained modification 4.0.01Cu 1.85stoichiometric proportion prepare burden, after mixing, in nitrogen atmosphere, 1000 DEG C of constant temperature 24h, obtain Cu 1.85the bulk phase-doped LiFePO of Se 4positive electrode.With LiFePO 4.0.01Cu 1.85for matrix, by Cu 1.78se is coated on blapharoplast surface, wherein LiFePO 4.0.01Cu 1.85and Cu 1.78the ratio of Se is 1:0.04.
Embodiment 4:
With the Cu of 1% 1.75se is configured to solution, is joined by lithium ferric manganese phosphate in this solution, and after mixing, heating evaporation is to forming gel, and 600 DEG C of constant temperature 2h obtain the lithium ferric manganese phosphate composite positive pole of modification.
The present invention is equally applicable to other lithium ion anode materials and Cu 2-xthe compound of Se (0.15≤x≤0.25) fast-ionic conductor, as lithium ferric manganese phosphate, nickel cobalt lithium aluminate, cobalt acid lithium or nickle cobalt lithium manganate.
Above content is only citing made for the present invention and explanation; affiliated those skilled in the art make various amendment to described specific embodiment or supplement or adopt similar mode to substitute; only otherwise depart from the design of invention or surmount this scope as defined in the claims, protection scope of the present invention all should be belonged to.

Claims (3)

1. material modified and preparation method thereof for lithium ion cell positive, it is characterized in that, described lithium ion battery comprises: positive plate, negative plate, be interval in barrier film between adjacent positive/negative plate and electrolyte; Described positive plate utilizes Cu 2-xse Material coating, wherein 0.15≤x≤0.25, carry out the modification of anode material for lithium-ion batteries.
2. material modified and preparation method thereof for lithium ion cell positive according to claim 1, is characterized in that, realize by one or more common implementings in following method:
(1) by Cu 2-xse (0.15≤x≤0.25) material is coated on positive electrode surface;
(2) by Cu 2-xse (0.15≤x≤0.25) material carries out bulk phase-doped modified to positive electrode;
(3) by Cu 2-xse (0.15≤x≤0.25) material carries out bulk phase-doped modified to positive electrode and is coated on positive electrode surface simultaneously;
(4) by Cu 2-xse (0.15≤x≤0.25) material and anode material for lithium-ion batteries are according to stoichiometric proportion, and after adopting solid phase method or liquid phase method to make the two mix, in atmosphere furnace, namely high temperature solid-phase sintering obtains the lithium ion battery composite cathode material of modification;
(5) by Cu 2-xse (0.15≤x≤0.25) and the raw material preparing positive electrode mix according to stoichiometric proportion to be prepared, namely obtain the lithium ion battery composite cathode material of modification through high temperature solid-phase sintering.
3. material modified and preparation method thereof for lithium ion cell positive according to claim 1, it is characterized in that, described anode material for lithium-ion batteries is one or more mixing in cobalt acid lithium, LiFePO4, lithium ferric manganese phosphate, LiMn2O4, nickle cobalt lithium manganate, nickel cobalt lithium aluminate, lithium nickel cobalt dioxide or nickel ion doped; Described Cu 2-xthe mol ratio of Se (0.15≤x≤0.25) material and positive electrode is 0.001-0.2:1.
CN201510611935.8A 2015-09-23 2015-09-23 Modified material for positive electrode of lithium ion battery and preparation method of modified material Pending CN105304905A (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107732247A (en) * 2017-11-14 2018-02-23 合肥国轩高科动力能源有限公司 A kind of lithium ion cell positive is material modified and preparation method thereof
CN108933257A (en) * 2018-08-31 2018-12-04 浙江大学 Cu as lithium ion battery electrode material2-xSe nano material and preparation method thereof
CN109755513A (en) * 2018-12-26 2019-05-14 格林美(无锡)能源材料有限公司 Metal selenide/C/B compound coating positive electrode and preparation method thereof
CN112700967A (en) * 2020-11-30 2021-04-23 电子科技大学 Cu with high specific capacity2-xNegative electrode material of Se super capacitor

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1773763A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion secondary cell with nickel-base anode active material and producing method thereof
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
US20110086272A1 (en) * 2009-10-13 2011-04-14 Kepler Keith D Li-ion battery and its preparation method
CN102738451A (en) * 2012-07-13 2012-10-17 河南师范大学 Modified positive electrode material of lithium ion battery and preparation method of modified positive electrode material
CN103887501A (en) * 2014-04-17 2014-06-25 哈尔滨工业大学 Method for preparing copper selenide lithium ion battery electrode material
CN104393234A (en) * 2014-11-21 2015-03-04 海宁美达瑞新材料科技有限公司 Modified lithium ion battery composite positive pole material and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1773763A (en) * 2004-11-08 2006-05-17 深圳市比克电池有限公司 Lithium ion secondary cell with nickel-base anode active material and producing method thereof
US20110086272A1 (en) * 2009-10-13 2011-04-14 Kepler Keith D Li-ion battery and its preparation method
CN101969110A (en) * 2010-08-31 2011-02-09 天津巴莫科技股份有限公司 Fast ion conductor modified lithium ion battery cathode material lithium cobalt oxide with fast ion conductor and preparation method
CN102738451A (en) * 2012-07-13 2012-10-17 河南师范大学 Modified positive electrode material of lithium ion battery and preparation method of modified positive electrode material
CN103887501A (en) * 2014-04-17 2014-06-25 哈尔滨工业大学 Method for preparing copper selenide lithium ion battery electrode material
CN104393234A (en) * 2014-11-21 2015-03-04 海宁美达瑞新材料科技有限公司 Modified lithium ion battery composite positive pole material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
A.N. SKOMOROKHOV等: "Structural behaviour of β-Cu2-δSe (δ = 0, 0.15, 0.25) in dependence on temperature studied by synchrotron powder diffraction", 《JOURNAL OF ALLOYS AND COMPOUNDS》 *
WEIXIN ZHANG等: "Chemical replacement route to Cu2-xSe-coated CuO nanotube array anode for enhanced performance in lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107732247A (en) * 2017-11-14 2018-02-23 合肥国轩高科动力能源有限公司 A kind of lithium ion cell positive is material modified and preparation method thereof
CN108933257A (en) * 2018-08-31 2018-12-04 浙江大学 Cu as lithium ion battery electrode material2-xSe nano material and preparation method thereof
CN109755513A (en) * 2018-12-26 2019-05-14 格林美(无锡)能源材料有限公司 Metal selenide/C/B compound coating positive electrode and preparation method thereof
CN112700967A (en) * 2020-11-30 2021-04-23 电子科技大学 Cu with high specific capacity2-xNegative electrode material of Se super capacitor

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Application publication date: 20160203