CN106935846A - A kind of preparation method of the modified nickel lithium manganate cathode material of high voltage - Google Patents

A kind of preparation method of the modified nickel lithium manganate cathode material of high voltage Download PDF

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Publication number
CN106935846A
CN106935846A CN201611269964.1A CN201611269964A CN106935846A CN 106935846 A CN106935846 A CN 106935846A CN 201611269964 A CN201611269964 A CN 201611269964A CN 106935846 A CN106935846 A CN 106935846A
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target product
mixture
preparation
high voltage
nickel
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CN201611269964.1A
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徐茂龙
黄红如
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HUIZHOU LONGWAYCAP TECHNOLOGY Co Ltd
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HUIZHOU LONGWAYCAP TECHNOLOGY Co Ltd
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Priority to CN201611269964.1A priority Critical patent/CN106935846A/en
Publication of CN106935846A publication Critical patent/CN106935846A/en
Priority to PCT/CN2017/110596 priority patent/WO2018121102A1/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
    • H01M4/36—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
    • 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)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of preparation method of the modified nickel lithium manganate cathode material of high voltage, comprises the following steps：(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；(2) the first mixture is added in having an ethylene glycol solution, obtains nickel manganese presoma；(3) nickel manganese presoma and lithium carbonate, metal oxide are mixed into obtain dopant mixture；(4) doping mixing is sintered, obtains pre-sintered mass；(5) pre-sintered mass is carried out into air-flow crushing and obtains pre- target product；(6) it is 1 according to mass ratio by pre- target product and Graphene:0.01~0.5 ratio is mixed, obtain target product, the present invention provide a kind of modified nickel lithium manganate cathode material of high voltage preparation method have efficiently, quick, energy-conservation the characteristics of, and the method process is simple, it is environment-friendly, be adapted to high-volume industry and produce.

Description

A kind of preparation method of the modified nickel lithium manganate cathode material of high voltage
Technical field
The present invention relates to a kind of method for preparing anode material, and in particular to a kind of high voltage is modified nickel lithium manganate cathode material Preparation method.
Background technology
Nickel ion doped is mainly spinel-type nickel ion doped, and chemical formula is represented by LiNi0.5Mn1.5O4, with another kind Referred to as binary lamellar structure compound (the chemical formula LiNi of nickel ion doped0.5Mn1.5O4) it is two kinds of lithium-ion electrics of structural system Pond positive electrode.
Spinel-type nickel ion doped grows up on the basis of lithium manganate having spinel structure, is have as LiMn2O4 The positive electrode of three-dimensional lithium ion tunnel, reversible capacity is 146.7mAh/g, similar with LiMn2O4, but voltage platform is 4.7V or so, cyclical stability under more than 15%, and high temperature will be higher by also than original manganese than the 4V voltage platforms of LiMn2O4 Sour lithium is improved.
Nickel ion doped is the anode material for lithium-ion batteries with attractive prospect just under development, with lithium cobaltate cathode material Material is compared, and its output voltage is high, low cost, environment-friendly；Compared with manganate cathode material for lithium, its stabilization under high temperature circulation Property is greatly improved；Compared with lithium iron phosphate cathode material, its preparation process is simple, the lot stability of production is good, particularly When matching with lithium titanate anode, LiFePO 4-lithium titanate cell only has 1.9V output voltages, and nickel ion doped- Lithium titanate cell output voltage may be up to 3.2V, advantage clearly, however as the development of automobile industry, power type nickel LiMn2O4 becomes the focus of people's research, how the challenge that to be people face of further booster tension platform and capacity.
The content of the invention
The technical problems to be solved by the invention are directed to above-mentioned the deficiencies in the prior art and provide a kind of efficient longevity Life, the preparation method of Hyperhemodynamics type manganate cathode material for lithium.
The present invention provides a kind of preparation method of the modified nickel lithium manganate cathode material of high voltage, comprises the following steps：
(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；
(2) the first mixture obtained by step (1) is added in having an ethylene glycol solution, is stirred, nickel is obtained after drying Manganese presoma；
(3) the nickel manganese presoma and lithium carbonate, metal oxide obtained by step (2) are mixed in ethylene glycol solution 0.5~14h, obtains dopant mixture；
(4) by obtained by step (3) dopant mixture load saggar, feeding pushed bat kiln be sintered, sintering process not between It is disconnected to be filled with oxygen, 400~500 DEG C of sintering temperature, 2~3h of constant temperature time, 900~1000 DEG C of junction temperature, constant temperature time 8~ 9h, obtains pre-sintered mass；
(5) pre-sintered mass obtained by step (4) is carried out into air-flow crushing, classification and obtains pre- target product；
(6) by the pre- target product and Graphene obtained by step (5) according to mass ratio be 1:0.01~0.5 ratio is carried out Mixing, obtains target product.
Further, in step (3), the metal oxide is Al2O3、CeO2、SC2O3In one or more mixed Close.
The beneficial effects of the present invention are：
The preparation method that the present invention provides a kind of modified nickel lithium manganate cathode material of high voltage has efficient, quick, energy-conservation The characteristics of, and by the nickel lithium manganate cathode material that the synthetic method synthesizes have capacity it is high (first charge-discharge capacity reach 200- 250mAh/g, alreadys exceed highest specific capacity 137.8mAh/g of the prior art), high-temperature stable, good cycle the advantages of, And the method process is simple, environment-friendly, suitable high-volume industry are produced.
Specific embodiment
Lower mask body illustrates embodiments of the present invention, and only for reference and explanation is used, and does not constitute and patent of the present invention is protected Protect the limitation of scope.
Embodiment 1
The present invention provides a kind of preparation method of the modified nickel lithium manganate cathode material of high voltage, comprises the following steps：
(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；
(2) the first mixture obtained by step (1) is added in having an ethylene glycol solution, is stirred, nickel is obtained after drying Manganese presoma；
(3) the nickel manganese presoma and lithium carbonate, metal oxide obtained by step (2) are mixed in ethylene glycol solution 0.5~14h, obtains dopant mixture；
(4) by obtained by step (3) dopant mixture load saggar, feeding pushed bat kiln be sintered, sintering process not between It is disconnected to be filled with oxygen, 400~500 DEG C of sintering temperature, 2~3h of constant temperature time, 900~1000 DEG C of junction temperature, constant temperature time 8~ 9h, obtains pre-sintered mass；
(5) pre-sintered mass obtained by step (4) is carried out into air-flow crushing, classification and obtains pre- target product；
(6) by the pre- target product and Graphene obtained by step (5) according to mass ratio be 1:0.01~0.5 ratio is carried out Mixing, obtains target product.
In the present embodiment, in step (3), the metal oxide is Al2O3。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 200mAh/g, circulates 500 capability retentions up to 90%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 190mAh/g, circulates 500 capability retentions Up to 81%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 185mAh/g, circulates 500 capability retentions Up to 78%.
Embodiment 2
The present invention provides a kind of preparation method of the modified nickel lithium manganate cathode material of high voltage, comprises the following steps：
(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；
(2) the first mixture obtained by step (1) is added in having an ethylene glycol solution, is stirred, nickel is obtained after drying Manganese presoma；
(3) the nickel manganese presoma and lithium carbonate, metal oxide obtained by step (2) are mixed in ethylene glycol solution 0.5~14h, obtains dopant mixture；
(4) by obtained by step (3) dopant mixture load saggar, feeding pushed bat kiln be sintered, sintering process not between It is disconnected to be filled with oxygen, 400~500 DEG C of sintering temperature, 2~3h of constant temperature time, 900~1000 DEG C of junction temperature, constant temperature time 8~ 9h, obtains pre-sintered mass；
(5) pre-sintered mass obtained by step (4) is carried out into air-flow crushing, classification and obtains pre- target product；
(6) by the pre- target product and Graphene obtained by step (5) according to mass ratio be 1:0.01~0.5 ratio is carried out Mixing, obtains target product.
In the present embodiment, in step (3), the metal oxide is CeO2。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 210mAh/g, circulates 500 capability retentions up to 90%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 195mAh/g, circulates 500 capability retentions Up to 81%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 190mAh/g, circulates 500 capability retentions Up to 78%.
Embodiment 3
The present invention provides a kind of preparation method of the modified nickel lithium manganate cathode material of high voltage, comprises the following steps：
(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；
(2) the first mixture obtained by step (1) is added in having an ethylene glycol solution, is stirred, nickel is obtained after drying Manganese presoma；
(3) the nickel manganese presoma and lithium carbonate, metal oxide obtained by step (2) are mixed in ethylene glycol solution 0.5~14h, obtains dopant mixture；
(4) by obtained by step (3) dopant mixture load saggar, feeding pushed bat kiln be sintered, sintering process not between It is disconnected to be filled with oxygen, 400~500 DEG C of sintering temperature, 2~3h of constant temperature time, 900~1000 DEG C of junction temperature, constant temperature time 8~ 9h, obtains pre-sintered mass；
(5) pre-sintered mass obtained by step (4) is carried out into air-flow crushing, classification and obtains pre- target product；
(6) by the pre- target product and Graphene obtained by step (5) according to mass ratio be 1:0.01~0.5 ratio is carried out Mixing, obtains target product.
In the present embodiment, in step (3), the metal oxide is SC2O3。
Test result shows that, in charging/discharging voltage 2.0-4.75V, charge-discharge magnification is under the conditions of 0.5C, electric discharge first is compared Capacity is 250mAh/g, circulates 500 capability retentions up to 98%；
Under conditions of charge-discharge magnification is 1C, first discharge specific capacity is 240mAh/g, circulates 500 capability retentions Up to 90%；
Under conditions of charge-discharge magnification is 4C, first discharge specific capacity is 200mAh/g, circulates 500 capability retentions Up to 80%.
The preparation method that the present invention provides a kind of modified nickel lithium manganate cathode material of high voltage has efficient, quick, energy-conservation The characteristics of, and there is capacity high, high-temperature stable by the modified nickel lithium manganate cathode material of high voltage that the synthetic method synthesizes, follow The advantages of ring performance is good.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (2)

1. the preparation method of the modified nickel lithium manganate cathode material of a kind of high voltage, it is characterised in that comprise the following steps：
(1) manganese carbonate, nickelous carbonate are pressed into Mn:Ni mol ratios are 3:1 carries out dispensing is mixed to get the first mixture；
(2) the first mixture obtained by step (1) is added in having an ethylene glycol solution, is stirred, before nickel manganese is obtained after drying Drive body；
(3) the nickel manganese presoma and lithium carbonate, metal oxide obtained by step (2) are carried out into mixing 0.5 in ethylene glycol solution ~14h, obtains dopant mixture；
(4) dopant mixture obtained by step (3) is loaded into saggar, feeding pushed bat kiln is sintered, and sintering process is continual Oxygen is filled with, 400~500 DEG C of sintering temperature, 2~3h of constant temperature time, 900~1000 DEG C of junction temperature, 8~9h of constant temperature time is obtained Pre-sintered mass；
(5) pre-sintered mass obtained by step (4) is carried out into air-flow crushing, classification and obtains pre- target product；
(6) by the pre- target product and Graphene obtained by step (5) according to mass ratio be 1:0.01~0.5 ratio is mixed Close, obtain target product.
2. the preparation method of high voltage modification lithium-ion battery anode material nickel ion doped according to claim 1, it is special Levy and be：In step (3), the metal oxide is Al2O3、CeO2、SC2O3In the mixing of one or more.
CN201611269964.1A 2016-12-30 2016-12-30 A kind of preparation method of the modified nickel lithium manganate cathode material of high voltage Pending CN106935846A (en)

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PCT/CN2017/110596 WO2018121102A1 (en) 2016-12-30 2017-11-10 Method for preparing high-voltage modified lithium nickel manganese oxide anode material

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018121102A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing high-voltage modified lithium nickel manganese oxide anode material
CN112960704A (en) * 2021-02-01 2021-06-15 福建金山锂科新材料有限公司 Preparation method of high-voltage lithium nickel manganese oxide positive electrode material
CN113517437A (en) * 2021-07-14 2021-10-19 中国石油大学(北京) Cation modified spinel type lithium nickel manganese oxide and preparation method and application thereof
CN116216796A (en) * 2023-04-25 2023-06-06 荆门市格林美新材料有限公司 Modified nickel-manganese binary precursor and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114349072B (en) * 2021-12-27 2023-08-22 湖南海利锂电科技有限公司 High-voltage nickel-manganese binary positive electrode material and preparation method and application thereof
CN115465896A (en) * 2022-09-05 2022-12-13 江西智锂科技股份有限公司 Preparation method of high-stability lithium manganate

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CN104979549A (en) * 2015-07-29 2015-10-14 杭州朗鑫新材料科技有限公司 Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material
CN105322150A (en) * 2015-11-26 2016-02-10 中信大锰矿业有限责任公司大新锰矿分公司 Preparation technology of modified positive material lithium nickel manganese oxide for lithium-ion battery
CN105355905A (en) * 2015-11-26 2016-02-24 中信大锰矿业有限责任公司大新锰矿分公司 Method for preparing high-voltage modified lithium ion cell cathode material lithium nickel manganese oxide

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CN104466114A (en) * 2014-10-17 2015-03-25 惠州龙为科技有限公司 Preparation method of high-performance lithium manganite positive material
CN104979549A (en) * 2015-07-29 2015-10-14 杭州朗鑫新材料科技有限公司 Sheet lithium-enriched manganese-based anode material for lithium-ion battery as well as preparation method and application of sheet lithium-enriched manganese-based anode material
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018121102A1 (en) * 2016-12-30 2018-07-05 徐茂龙 Method for preparing high-voltage modified lithium nickel manganese oxide anode material
CN112960704A (en) * 2021-02-01 2021-06-15 福建金山锂科新材料有限公司 Preparation method of high-voltage lithium nickel manganese oxide positive electrode material
CN113517437A (en) * 2021-07-14 2021-10-19 中国石油大学(北京) Cation modified spinel type lithium nickel manganese oxide and preparation method and application thereof
CN116216796A (en) * 2023-04-25 2023-06-06 荆门市格林美新材料有限公司 Modified nickel-manganese binary precursor and preparation method and application thereof

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