CN104993106B - A kind of Zinc-base compounded material basic zinc carbonate and its preparation method and application - Google Patents
A kind of Zinc-base compounded material basic zinc carbonate and its preparation method and application Download PDFInfo
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- CN104993106B CN104993106B CN201510278225.8A CN201510278225A CN104993106B CN 104993106 B CN104993106 B CN 104993106B CN 201510278225 A CN201510278225 A CN 201510278225A CN 104993106 B CN104993106 B CN 104993106B
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- zinc
- ion battery
- lithium ion
- zinc carbonate
- basic zinc
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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
- H01M4/364—Composites as mixtures
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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
- 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
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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
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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
- H01M4/58—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
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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- 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 present invention provides a kind of Zinc-base compounded material, which is basic zinc carbonate（Zn5(CO3)2(OH)6）, its pattern is sheet；Its preparation method is：By the zinc acetate, sodium fluoride, hexamethylenetetramine in molar ratio 1 that purity is 99.9%：1：1 ~ 5 weighs；Raw material is positioned in container again plus distilled water stirs 30 minutes, forms homogeneous solution；Further obtained homogeneous solution is transferred in hydrothermal reaction kettle when 120 DEG C of reactions 12 ~ 24 are small, reaction product is centrifuged, drying to basic zinc carbonate lithium ion battery negative material.Obtained Zinc-base compounded material basic zinc carbonate is applied to prepare on lithium ion battery negative material by the present invention first.Synthetic method is simple, of low cost；Prepared basic zinc carbonate is sheet-like morphology, 3 ~ 10 mm of size, about 200 nm of average thickness；Material prepared has obvious charge and discharge platform, there is potential application in lithium ion battery.
Description
Technical field
The present invention relates to a kind of novel cathode material for lithium ion battery and preparation method thereof, more particularly to a kind of basic carbonate
Zinc belongs to electrochemistry field of novel as lithium ion battery negative material application and preparation method thereof.
Technical background：
Lithium ion battery is the third generation small battery after nickel-cadmium cell, Ni-MH battery, has operating voltage
Height, specific capacity is high, and specific power is big, and charge and discharge potential curve is steady, has extended cycle life, and memory-less effect, self discharge is small, environment friend
The advantages that good, be widely used to the Mobile portable equipments such as laptop, mobile phone at present.And following electric vehicle
Ideal power source.However, at present, the energy density of lithium ion battery, power density still cannot meet that it is produced in portable electronic piece
Product field and the requirement in power battery field, research and development novel high-energy metric density, high power density lithium ion battery be promote its
The basis of different field broader applications, and this depends on the research and development of high power capacity, high rate capability electrode material.Zinc-base composite wood
Material is since its is of low cost, rich reserves, advantages of environment protection become a kind of very attractive novel anode material.Example
Such as zinc manganate, cobalt acid zinc, zinc ferrite and Zinc vanadate show excellent electrochemistry as lithium ion battery plus-negative plate material
Performance.
Zn5(CO3)2(OH)6It is a kind of typical Zinc-base compounded material, on Zn5(CO3)2(OH)6Materials application mainly has：
Document [Yang LY, Feng GP, Wang TX, Mater.Lett.2010；64:1647-1649], [Bai HX, Liu XH,
Mater.Lett.2010；64:341-343], [Yan CL, Xue DF, J.Phys.Chem.B 2006,110,11076-
11080] reported with document [Jing ZH, Zhang JH, Adv.Mater.2008,20,4547-4551] by Zn5(CO3)2
(OH)6As synthesis ZnO2, ZnO precursor material；At present, the electrochemistry of negative electrode of lithium ion battery is used as on the compound
There is not been reported for performance study report.Based on background above, a kind of Zn of invention5(CO3)2(OH)6The preparation of micron film is newly square
Method, charge and discharge platform has been shown substantially using it as negative electrode of lithium ion battery, and it is potential to show that it has in lithium ion battery
Application value.
Goal of the invention
It is an object of the invention to using zinc acetate, sodium fluoride and hexamethylenetetramine as raw material, piece is prepared by hydro-thermal method
Shape lithium ion battery negative material Zn5(CO3)2(OH)6.Its principle is exactly to be promoted using the high temperature under hydrothermal condition, hyperbaric environment
Chemical reaction process in solution, so as to prepare the good sheet Zn of crystal property5(CO3)2(OH)6。
Reaction principle is：
C4H6O4Zn→Zn2++2[CH3COO]- (1)
(CH2)6N4+10H2O→6HCHO+4OH-+4[NH4]+ (2)
HCHO+O2+2OH-→CO3 2-+2H2O (3)
5Zn2++2CO3 2-+6OH-→Zn5(CO3)2(OH)6 (4)
Zn according to the present invention5(CO3)2(OH)6Synthesis material is zinc acetate, sodium fluoride and hexamethylenetetramine.Material
In preparation process, by the zinc acetate, sodium fluoride, hexamethylenetetramine in molar ratio 1 that purity is 99.9%：1：1~5 weighs；Again
Raw material is positioned in container plus distilled water stirs 30 minutes, forms homogeneous solution；Homogeneous solution is transferred to hydrothermal reaction kettle
In in 120 DEG C reaction 12~24 it is small when, reaction product is centrifuged, drying to Zn5(CO3)2(OH)6Negative electrode of lithium ion battery
Material.The pattern of the negative material is sheet.
The present invention uses Zinc-base compounded material Zn made from above-mentioned technical proposal5(CO3)2(OH)6First Application is in preparing lithium
In ion battery cathode material.
Zn according to the present invention5(CO3)2(OH)6Negative material and preparation method have following distinguishing feature：
(1) synthetic method is simple, of low cost；
(2) Zn prepared by5(CO3)2(OH)6For sheet-like morphology, 3~10 μm of size, average thickness about 200nm；
(3) material prepared has obvious charge and discharge platform, there is potential application in lithium ion battery.
Brief description of the drawings
The XRD spectrum of sample prepared by Fig. 1 embodiments；
(a) low power of sample prepared by Fig. 2 embodiments, (b) high power SEM figures；
(a) of sample prepared by Fig. 3 embodiments charge and discharge curve and (b) cycle performance figure first.
Embodiment
Embodiment 1
The zinc acetate, sodium fluoride, hexamethylenetetramine of purity 99.9% are weighed into 1mmol, 1mmol, 5mmol respectively, put
It is placed in beaker plus distilled water stirs evenly, when being transferred in high pressure hydro-thermal axe that reaction 24 is small at 120 DEG C, reaction product is used
Alcohol, distilled water eccentric cleaning, are transferred in culture dish and dry derived sample.Prepared sample is such as schemed through XRD diagram spectrum analysis
Shown in 1, at 13.1 °, 16.6 °, 22.3 °, 24.3 °, 28.4 °, 29.7 °, 30.6 °, 31.4 °, 32.9 °, 33.3 °, 34,8 °,
36.2 °, 39.1 °, 41 °, 43.4 °, 47.8 °, 50.3 °, 51.5 °, 54.4 °, 55.4 °, 58.7 °, 59.8 °, 63.4 °, 68.6 ° and
69.9 ° of diffraction maximums can be with monoclinic system Zn5(CO3)2(OH)6(200), (001), (- 111), (310), (020), (- 401),
(311),(220),(021),(002),(-202),(510),(420),(-402),(312),(330),(-331),(-621),
(800), (- 801), (- 622) (- 223), (- 821), (- 133) are corresponding with (- 204) crystal face, and standard card JCPDS,
No.19-1458 is consistent.Prepared sample is characterized through SEM, as shown in Fig. 2 (a), is made of a large amount of sheet-like morphologies, its length point
Cloth is 3~10 μm or so, and thickness is in 200nm or so.Be further amplified by Fig. 2 (b) it can be seen that piece thickness for 100~
300nm.Battery is made in material obtained by embodiment as follows：By obtained Zn5(CO3)2(OH)6Sample and natural stone
Ink 1：1 is uniformly mixed, then by Zn5(CO3)2(OH)6/ native graphite composite material and acetylene black and Kynoar are by weight
For 8:1:1 ratio mixing, is made slurry, on the copper foil coated in 10 μ m thicks, 60 by solvent of 1-methyl-2-pyrrolidinone
After when drying 10 is small at DEG C, the disk of 14mm is cut into, when vacuum drying 12 is small at 120 DEG C.Using metal lithium sheet as to electrode,
Celgard films are membrane, dissolved with LiPF6EC+DMC+DEC (the volume ratios 1 of (1mol/L):1:1) solution is electrolyte,
CR2025 type batteries are assembled into the glove box of argon gas protection.Battery pack stood after installing 8 it is small when, then with CT2001A batteries
Test system carries out constant current charge and discharge test, and test voltage is 3~0.02V.If Fig. 3 is prepared sheet lithium ion battery
Negative material Zn5(CO3)2(OH)6The curve of charge and discharge first and cycle performance of/native graphite composite material, it fills, puts first
Electric specific capacity is respectively 428.1,1248.2mAh/g, and charge and discharge capacity is respectively 297.4,302mAh/g after 100 circulations,
Show that it has potential application value in lithium ion battery.
Claims (1)
1. a kind of lithium ion battery negative material, it is characterised in that the negative material is Zinc-base compounded material, the composite wood
Expect for basic zinc carbonate Zn5(CO3)2(OH)6, its pattern is sheet；
The Zinc-base compounded material basic zinc carbonate Zn5(CO3)2(OH)6Preparation method be：
（1）By the zinc acetate, sodium fluoride, hexamethylenetetramine in molar ratio 1 that purity is 99.9%：1：5 weigh；
（2）By step（1）In the raw material that weighs be positioned in container plus distilled water stirs 30 minutes, form homogeneous solution；
（3）By step（2）Homogeneous solution be transferred in hydrothermal reaction kettle in 120 DEG C reaction 12 ~ 24 it is small when, by reaction product from
The heart, drying to Zn5(CO3)2(OH)6Lithium ion battery negative material；
Prepared sample is characterized through SEM, is made of a large amount of sheet-like morphologies, its distribution of lengths is 3 ~ 10 μm, and average thickness is
200 nm。
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| CN104993106B true CN104993106B (en) | 2018-05-08 |
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| CN106848281B (en) * | 2017-01-19 | 2019-06-11 | 江苏理工学院 | A kind of negative electrode material of zinc-nickel cell and preparation method thereof and purposes |
| CN106684362B (en) * | 2017-01-19 | 2019-05-07 | 江苏理工学院 | A kind of zinc-nickel battery anode material |
| CN108735517B (en) * | 2018-05-30 | 2020-09-25 | 大连交通大学 | Basic zinc carbonate supercapacitor electrode material and preparation method thereof |
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