CN105702922A - Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste - Google Patents

Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste Download PDF

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Publication number
CN105702922A
CN105702922A CN201610042420.5A CN201610042420A CN105702922A CN 105702922 A CN105702922 A CN 105702922A CN 201610042420 A CN201610042420 A CN 201610042420A CN 105702922 A CN105702922 A CN 105702922A
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China
Prior art keywords
zinc oxide
lithium ion
ion battery
grapheme modified
negative electrode
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Pending
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CN201610042420.5A
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Chinese (zh)
Inventor
汪训国
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ZHEJIANG JILI POWER NEW ENERGY CO Ltd
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ZHEJIANG JILI POWER NEW ENERGY CO Ltd
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Priority to CN201610042420.5A priority Critical patent/CN105702922A/en
Publication of CN105702922A publication Critical patent/CN105702922A/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
    • H01M4/362—Composites
    • 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
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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

Abstract

The invention discloses a zinc oxide modified graphene negative electrode paste of a lithium ion battery and a preparation method of the negative electrode paste. The zinc oxide modified graphene negative electrode paste of the lithium ion battery comprises the following constituents: 15-45% of zinc oxide modified graphene, 1.5-3.5% of conductive material, 1-2.5% of dispersing agent, 0.6-1.5% of binding agent and the balance of solvent. The brand-new zinc oxide modified graphene material is applied to the negative electrode paste of the lithium ion battery, thus, reasonable proportion between an active substance and other auxiliary materials is provided. By the zinc oxide modified graphene negative electrode paste, a reasonable and reliable formula is provided for actual application of the zinc oxide modified graphene material, and the excellent performance of the new material can be fully developed.

Description

A kind of grapheme modified lithium ion battery cathode slurry of zinc oxide and preparation method thereof
Technical field
The invention belongs to technical field of lithium-ion battery, it is specifically related to a kind of grapheme modified lithium ion battery cathode slurry of zinc oxide and preparation method thereof, especially, the present invention by the brand-new grapheme modified materials application of zinc oxide in lithium ion battery negative, to improve the performance of lithium ion battery。
Background technology
Graphite is the main negative material of current commercial li-ion battery, in charging process, forms the intercalation compound of graphite and lithium in Lithium-ion embeding graphite。Graphite has good charging/discharging voltage platform, and theoretical capacity is 372mAh/g, simultaneously as the time of Lithium-ion embeding graphite layers is longer, thus the charge/discharge rates of graphite electrode is slower。In recent years, along with mobile electronic device is more and more higher to the requirement of power supply flying power and charging interval, traditional graphite electrode can not meet the requirement of high performance lithium ion battery。In this context, Graphene becomes the focus material of lithium cell cathode material due to the character such as high conductivity and high-specific surface area。With graphite-phase ratio, lithium ion can be adsorbed respectively in the both sides of Graphene atomic layer, and therefore, single-layer graphene theoretical capacity can reach the twice of graphite, for 744mAh/g。Further, since the increase of porosity between graphene sheet layer, the absorption of lithium ion and desorption process can be very quick。
Applying for negative pole, zinc oxide has the theoretical capacity times over material with carbon element。But there is a fatal defect as the negative material of lithium ion battery in zinc oxide material, it is exactly in the absorption and desorption process of lithium ion, change in volume is big, bigger stress can destroy conductive path, cause that charge and discharge cycles forms extreme difference, it addition, the electron mobility of zinc oxide is relatively low, cause lithium ion battery internal resistance bigger。
Summary of the invention
Based on above-mentioned prior art, the invention provides a kind of grapheme modified lithium ion battery cathode slurry of zinc oxide and preparation method thereof, it obtains the Graphene negative material as lithium ion battery of zinc oxide modification by single step reaction method, fully in conjunction with the advantage of zinc oxide specific capacity height and Graphene high conductivity, high-specific surface area, it is thus achieved that the negative material that capacity is high, charge/discharge rates is fast。
The present invention takes techniques below scheme:
A kind of grapheme modified lithium ion battery cathode slurry of zinc oxide, it comprises the component of following ratio:
Zinc oxide grapheme modified 15% ~ 45%, conductive material 1.5% ~ 3.5%, dispersant 1% ~ 2.5%, binding agent 0.6% ~ 1.5%, surplus is solvent。
Preferably, the gram volume that zinc oxide is grapheme modified is more than 1400mAh/g。
Preferably, conductive material is conductive black, electrically conductive graphite or in acetylene black one or more mixing。
Preferably, dispersant is sodium carboxymethyl cellulose (CMC)。
Preferably, binding agent is butadiene-styrene rubber (SBR)。
Preferably, solvent is water。
Preferably, the solid content of slurry is 15% ~ 60%。
The preparation steps of the grapheme modified lithium ion battery cathode slurry of above-mentioned zinc oxide:
(1) first the solvent of aequum 70% ~ 90% such as water is put in agitator, add the desired amount of dispersant such as CMC, stir 5 ~ 6 hours；
(2) dispersant dissolves after completely and adds the desired amount of binding agent such as SBR, stirs 1 ~ 2 hour；
(3), after binding agent dispersion completely, add the desired amount of conductive agent, stir 1 ~ 2 hour；
(4), after conductive agent dispersion completely, it is grapheme modified to add the desired amount of zinc oxide, stirs 5 ~ 6 hours。After all components dispersion completely, add residual solvent and adjust slurry solid content to 15% ~ 60%。
The present invention by the brand-new grapheme modified materials application of zinc oxide in lithium ion battery cathode slurry, it is provided that rational proportioning between active substance and other adjuvant。The present invention is for the zinc oxide actually used offer of grapheme modified material rationally reliable formula, is that the premium properties of new material is given full play to。
Detailed description of the invention
Below the preferred embodiment of the present invention is elaborated。
Embodiment 1
The grapheme modified lithium ion battery cathode slurry of zinc oxide, comprises the component of following ratio: the zinc oxide grapheme modified 15% of gram volume 2000mAh/g, conductive black 1.5%, sodium carboxymethyl cellulose 1%, butadiene-styrene rubber 0.6%, surplus is water。The solid content of slurry is 15%。
Embodiment 2
The grapheme modified lithium ion battery cathode slurry of zinc oxide, comprises the component of following ratio: the zinc oxide grapheme modified 45% of gram volume 1800mAh/g, electrically conductive graphite 3.5%, sodium carboxymethyl cellulose 2.5%, butadiene-styrene rubber 1.5%, surplus is water。The solid content of slurry is 60%。
Embodiment 3
The grapheme modified lithium ion battery cathode slurry of zinc oxide, comprises the component of following ratio: the gram volume zinc oxide more than 1400mAh/g grapheme modified 30%, acetylene black 2.5%, sodium carboxymethyl cellulose 2%, butadiene-styrene rubber 1%, and surplus is water。The solid content of slurry is 30%。
Embodiment 4
The preparation steps of the grapheme modified lithium ion battery cathode slurry of zinc oxide:
(1) first the solvent of aequum 85% such as water is put in agitator, add the dispersing agent C MC of 1.%, stir 5 ~ 6 hours；
(2) dispersant dissolves the binding agent SBR adding 0.9% after completely, stirs 1 ~ 2 hour；
(3), after binding agent dispersion completely, add the conductive agent of 3%, stir 1 ~ 2 hour；
(4), after conductive agent dispersion completely, it is grapheme modified to add 35% gram volume zinc oxide more than 1400mAh/g, stirs 5 ~ 6 hours。After all components dispersion completely, add residual solvent and adjust slurry solid content to 50%。
Embodiment 5
The preparation steps of the grapheme modified lithium ion battery cathode slurry of zinc oxide:
(1) first the solvent of aequum 80% such as water is put in agitator, add the dispersing agent C MC of 1.5%, stir 5 ~ 6 hours；
(2) dispersant dissolves the binding agent SBR adding 1.2% after completely, stirs 1 ~ 2 hour；
(3), after binding agent dispersion completely, add the conductive agent of 2%, stir 1 ~ 2 hour；
(4), after conductive agent dispersion completely, it is grapheme modified to add 40% gram volume zinc oxide more than 1400mAh/g, stirs 5 ~ 6 hours。After all components dispersion completely, add residual solvent and adjust slurry solid content to 20%。
The features such as Graphene slurry provided by the invention has good conductivity, gram volume is high, equipment is simple, cost is low, applied widely, cannot be only used on mobile device product, it is also possible to be applied in New-energy electric vehicle and energy storage lithium ion battery。

Claims (10)

1. the grapheme modified lithium ion battery cathode slurry of zinc oxide, is characterized in that comprising the component of following ratio: zinc oxide grapheme modified 15% ~ 45%, conductive material 1.5% ~ 3.5%, dispersant 1% ~ 2.5%, binding agent 0.6% ~ 1.5%, surplus is solvent。
2. the grapheme modified lithium ion battery cathode slurry of zinc oxide as claimed in claim 1, is characterized in that: the grapheme modified gram volume of described zinc oxide is more than 1400mAh/g。
3. the grapheme modified lithium ion battery cathode slurry of zinc oxide as claimed in claim 1, is characterized in that: described dispersant is sodium carboxymethyl cellulose。
4. the grapheme modified lithium ion battery cathode slurry of zinc oxide as claimed in claim 1, is characterized in that: described binding agent is butadiene-styrene rubber。
5. the grapheme modified lithium ion battery cathode slurry of zinc oxide as claimed in claim 1, is characterized in that: one or more mixing in conductive black, electrically conductive graphite or acetylene black selected by described conductive material。
6. the grapheme modified lithium ion battery cathode slurry of zinc oxide as claimed in claim 1, is characterized in that: described solvent is water。
7. the grapheme modified lithium ion battery cathode slurry of zinc oxide as described in any one of claim 1-6, is characterized in that: the solid content of described slurry is 15% ~ 60%。
8. a preparation method for the grapheme modified lithium ion battery cathode slurry of zinc oxide as described in any one of claim 1-6, is characterized in that as follows:
(1) first the solvent of aequum 70% ~ 90% is put in agitator, add the dispersant of 1% ~ 2.5%；
(2) dispersant dissolves the binding agent adding 0.6% ~ 1.5% after completely；
(3), after binding agent dispersion completely, the conductive material of 1.5% ~ 3.5% is added；
(4), after conductive agent dispersion completely, the zinc oxide of addition 15% ~ 45% is grapheme modified；After all components dispersion completely, add residual solvent and adjust slurry solid content to 15% ~ 60%。
9. preparation method as claimed in claim 8, is characterized in that: step (1), step (4), respectively stirs 5 ~ 6 hours。
10. preparation method as claimed in claim 8, is characterized in that: step (2), step (3), respectively stirs 1 ~ 2 hour。
CN201610042420.5A 2016-01-22 2016-01-22 Zinc oxide modified graphene negative electrode paste of lithium ion battery and preparation method of negative electrode paste Pending CN105702922A (en)

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CN106450336A (en) * 2016-12-06 2017-02-22 先进储能材料国家工程研究中心有限责任公司 Lithium ion battery negative electrode slurry and preparation method thereof
CN107634192A (en) * 2017-08-23 2018-01-26 北京航空航天大学 A kind of zinc-base negative electrode battery material and preparation method thereof
CN114784242A (en) * 2022-04-13 2022-07-22 内蒙古欣源石墨烯科技股份有限公司 Preparation method of nano-carbon coated lithium battery negative electrode material

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CN103545526A (en) * 2013-09-25 2014-01-29 东莞市翔丰华电池材料有限公司 Preparation method of aqueous lanthanum-doped lithium titanate anode paste
CN104167537A (en) * 2014-09-12 2014-11-26 杭州电子科技大学 Graphene/zinc oxide negative electrode material for lithium ion battery, and preparation method thereof
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CN101901932A (en) * 2010-05-17 2010-12-01 江西省福斯特新能源有限公司 Quick-chargeable, high-security and high-multiplying-power battery and production method thereof
CN103545526A (en) * 2013-09-25 2014-01-29 东莞市翔丰华电池材料有限公司 Preparation method of aqueous lanthanum-doped lithium titanate anode paste
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106450336A (en) * 2016-12-06 2017-02-22 先进储能材料国家工程研究中心有限责任公司 Lithium ion battery negative electrode slurry and preparation method thereof
CN106450336B (en) * 2016-12-06 2019-07-02 先进储能材料国家工程研究中心有限责任公司 A kind of lithium ion battery anode slurry and preparation method thereof
CN107634192A (en) * 2017-08-23 2018-01-26 北京航空航天大学 A kind of zinc-base negative electrode battery material and preparation method thereof
CN107634192B (en) * 2017-08-23 2020-09-11 北京航空航天大学 Negative electrode material for zinc-based battery and preparation method thereof
CN114784242A (en) * 2022-04-13 2022-07-22 内蒙古欣源石墨烯科技股份有限公司 Preparation method of nano-carbon coated lithium battery negative electrode material

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Application publication date: 20160622