CN110408043A - A kind of tinbase coordination polymer lithium ion battery negative material and preparation method thereof - Google Patents

A kind of tinbase coordination polymer lithium ion battery negative material and preparation method thereof Download PDF

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Publication number
CN110408043A
CN110408043A CN201910571262.6A CN201910571262A CN110408043A CN 110408043 A CN110408043 A CN 110408043A CN 201910571262 A CN201910571262 A CN 201910571262A CN 110408043 A CN110408043 A CN 110408043A
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tinbase
lithium ion
ion battery
coordination polymer
battery negative
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CN110408043B (en
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曾丹黎
刘光鹏
陈宇轩
陈奇
张斌
张俊峰
张舜
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China University of Geosciences
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China University of Geosciences
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008Supramolecular polymers
    • HELECTRICITY
    • H01ELECTRIC 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
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/60Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602Polymers
    • H01M4/604Polymers containing aliphatic main chain polymers
    • HELECTRICITY
    • H01ELECTRIC 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
    • H01M2004/026Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027Negative electrodes
    • 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

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  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Organic Chemistry (AREA)
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Abstract

The present invention relates to lithium ion battery preparation fields, a kind of tinbase coordination polymer lithium ion battery negative material and preparation method thereof is specifically disclosed, the raw material components of the tinbase coordination polymer lithium ion battery negative material include: tin source, activator, organic ligand and liquid solvent.Using alkaline activation reagent, by organic ligand in-situ preparation salting liquid, not only the yield of coordination polymer, environment-friendly high-efficiency can also can be improved in the reaction using water as solvent in the present invention.The tinbase coordination polymer of the method preparation provided through the invention can be used as lithium secondary battery cathode material application, have preferable cyclical stability.

Description

A kind of tinbase coordination polymer lithium ion battery negative material and preparation method thereof
Technical field
The invention belongs to technical field of lithium ion, in particular to a kind of tinbase coordination polymer negative electrode of lithium ion battery Material and preparation method thereof.
Background technique
Coordination polymer, due to its unique structure, organic ligand separates metal ion, provides for metal ion larger Space, so as to avoid contacting with each other between metal or reunite, this advantage is for the lithium ion with bulk effect Cell negative electrode material is of great significance.But the preparation of current coordination polymer is there are two problem, one, using organic solvent not Conducive to environment;Two, yield is lower.Therefore, exploitation environmental protection, economic coordination polymer preparation method seem particularly significant.
Carbonaceous material, such as hard carbon, graphite etc. are the common negative electrode materials of lithium ion battery, but its theoretical specific capacity compared with Low, therefore, attention is transferred on the non-carbon negative material of Novel high-specific capacity flexible by researcher, wherein tin base cathode material because Its resourceful, environmental-friendly and high theoretical specific capacity is expected to become next-generation lithium ion battery negative material.However, tin Volume expansion problem of the base negative electrode material in charge and discharge process causes battery capacity constantly to decay, thus hinder its lithium from Practical application in sub- battery.
Summary of the invention
In view of the above technical problems, the present invention provides a kind of tinbase coordination polymer lithium ion battery negative material and its Preparation method, the tinbase coordination polymer lithium ion battery negative material have height ratio capacity and excellent cyclical stability.
In order to achieve the above object, the present invention is achieved by the following scheme.The present invention provides a kind of tinbase and matches Including following raw material components: position polymer Li-ion battery negative electrode material organic ligand, activator, tin source and can dissolve State the liquid solvent of raw material.
Preferably, the organic ligand is the aliphatic small molecule containing more than two carboxyls.
Preferably, the aliphatic small molecule can be oxalic acid HOOC-COOH, succinic acidMaleic acidFumaric acidWine Stone acidOr citric acidDeng it is any.
Preferably, the activator can be any one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
Preferably, the tin source is stannic chloride pentahydrate.
Preferably, the liquid solvent is deionized water.
The present invention also provides the preparation method of above-mentioned tinbase coordination polymer lithium ion battery negative material, including it is following Step:
S1, weighs activator and is dissolved in liquid solvent and form the first solution;
S2 weighs organic ligand and is dissolved in liquid solvent and mixes with the first solution, and constant temperature stirs evenly, and it is molten to form second Liquid;
S3 weighs tin source and is dissolved in formation third solution in liquid solvent, third solution is added in the second solution, is mixed Solution afterwards becomes cloudy;Mixed solution is transferred in hydrothermal reaction kettle, heated at constant temperature certain time, natural cooling, from The heart is dried to get negative electrode material is arrived.
Preferably, the heating temperature of the heated at constant temperature is 110 DEG C, and reaction can be normally carried out and avoid reacting at a temperature of this Air pressure is excessively high and generate safety problem in kettle.
Preferably, the heating time of the heated at constant temperature is 24 hours, which can carry out to complete the reaction.
The present invention utilizes lithium hydroxide lithiumation organic ligand, improves its reactivity, it can be filled with metal tin ion Divide reaction, then compressive reaction obtains tinbase coordination polymer lithium ion battery negative material in reaction kettle.
Tinbase coordination polymer lithium ion battery negative material prepared by the present invention, by it with conductive agent and bonding agent according to Ratio mixing, is added appropriate solvent, is coated in the electrode use that can be used as battery on copper foil after mixing evenly.
Compared with prior art, the present invention having the following advantages that and beneficial technical effect: the activator that the present invention uses Organic ligand not soluble in water can be made to be dissolved in water in the form of carboxylate, therefore, the solvent used in preparation process need to only be gone Ionized water, environmental protection are easy to get;The activator that the present invention uses can effectively improve the reactivity of organic ligand, thus substantially Improve the yield of tinbase coordination polymer.
Detailed description of the invention
Fig. 1 is the X-ray diffraction of tinbase coordination polymer lithium ion battery negative material prepared by the embodiment of the present invention 2 Figure.
Fig. 2 is the scanning electron microscope (SEM) photograph of tinbase coordination polymer lithium ion battery negative material prepared by the embodiment of the present invention 2.
Fig. 3 is that the cyclic voltammetric of tinbase coordination polymer lithium ion battery negative material prepared by the embodiment of the present invention 2 is bent Line chart.
Fig. 4 is that the cycle performance of tinbase coordination polymer lithium ion battery negative material prepared by the embodiment of the present invention 2 is bent Line chart.
Specific embodiment
The present invention is described in further details combined with specific embodiments below, but the present invention is not limited to these Examples.
Embodiment 1:
(1) 10mmol succinic acid and 20mmol lithium hydroxide are dissolved in respectively in 10mL and 20mL deionized water, then will The two mixing, obtains colourless transparent solution;
(2) 10mmol stannic chloride pentahydrate is dissolved in 10mL deionized water, obtains tin tetrachloride solution, then by tetrachloro Change solution of tin to be all added drop-wise in above-mentioned colourless transparent solution, mixed solution becomes cloudy;
(3) above-mentioned mixed turbid solution is transferred in the reaction kettle of 100mL polytetrafluoroethyllining lining, by reaction kettle It is placed in baking oven, 110 DEG C are reacted 24 hours, cooled to room temperature, and centrifugation respectively washs number with deionized water and dehydrated alcohol It is secondary, it is dried in vacuo 24 hours at 100 DEG C, obtains negative electrode material.
Embodiment 2:
(1) 10mmol Citric Acid Mono and 30mmol lithium hydroxide are dissolved in respectively in 10mL and 30mL deionized water, so The two is mixed afterwards, obtains colourless transparent solution;
(2) 10mmol stannic chloride pentahydrate is dissolved in 10mL deionized water, obtains tin tetrachloride solution, then by tetrachloro Change solution of tin to be all added drop-wise in above-mentioned colourless transparent solution, mixed solution becomes cloudy;
(3) above-mentioned mixed turbid solution is transferred in the reaction kettle of 100mL polytetrafluoroethyllining lining, by reaction kettle It is placed in baking oven, 110 DEG C are reacted 24 hours, cooled to room temperature, and centrifugation respectively washs number with deionized water and dehydrated alcohol It is secondary, it is dried in vacuo 24 hours at 100 DEG C, obtains negative electrode material.
Fig. 1 is the X-ray diffractogram of tinbase coordination polymer lithium ion battery negative material prepared by embodiment 2, is passed through Comparative analysis is it is found that the diffraction maximum and space group of tinbase coordination polymer lithium ion battery negative material are the dioxy of P42/mnm (110), (101), (211) and (112) crystal face for changing tin coincides, and it is similar with stannic oxide to show that the negative electrode material has Crystal structure.
Fig. 2 is the scanning electron microscope (SEM) photograph of tinbase coordination polymer lithium ion battery negative material prepared by embodiment 2, from Fig. 2 In as can be seen that block-like tinbase coordination polymer equably pile up together, size range be 4-10 μm.
Fig. 3 is the tinbase coordination polymer lithium ion battery negative material of the preparation of embodiment 2 in 0.1mV s-1Sweep under speed Cyclic voltammetry curve, by curve in Fig. 3 it is found that the electrochemical behavior of battery is the redox based on metallic tin.
Fig. 4 is the tinbase coordination polymer lithium ion battery negative material of the preparation of embodiment 2 in 100mA g-1Electric current it is close Cycle performance curve under degree, although following for 30 times figure 4, it is seen that the capacity of preceding 30 cycle batteries constantly reduces The capacity of battery is without significant change after ring, and after 200 times recycle, capacity is still up to 637.5mAh g-1, accordingly, 30 circulations Afterwards, the coulombic efficiency of battery is all larger than 99%.
Embodiment 3:
(1) 10mmol fumaric acid and 20mmol lithium hydroxide are dissolved in respectively in 10mL and 20mL deionized water, then will The two mixing, obtains colourless transparent solution;
(2) 10mmol stannic chloride pentahydrate is dissolved in 10mL deionized water, obtains tin tetrachloride solution, then by tetrachloro Change solution of tin to be all added drop-wise in above-mentioned colourless transparent solution, mixed solution becomes cloudy;
(3) above-mentioned mixed turbid solution is transferred in the reaction kettle of 100mL polytetrafluoroethyllining lining, by reaction kettle It is placed in baking oven, 110 DEG C are reacted 24 hours, cooled to room temperature, and centrifugation respectively washs number with deionized water and dehydrated alcohol It is secondary, it is dried in vacuo 24 hours at 100 DEG C, obtains negative electrode material.
Tinbase coordination polymer lithium ion battery negative material prepared by embodiment 1 and embodiment 3, performance and embodiment The negative electrode active material of 2 preparations is suitable, equally shows height ratio capacity, high charge-discharge efficiencies and good cyclical stability.
The above is only preferable case of the invention, does not make any restrictions to the present invention, all for the present invention Any simple modification, alteration or imitation that technology contents do the above case study on implementation belongs to the protection of technical solution of the present invention Range.

Claims (9)

1. a kind of tinbase coordination polymer lithium ion battery negative material, which is characterized in that including following raw material components: You Jipei Body, activator, tin source and liquid solvent.
2. a kind of tinbase coordination polymer lithium ion battery negative material according to claim 1, which is characterized in that described Organic ligand is the aliphatic small molecule containing more than two carboxyls.
3. a kind of tinbase coordination polymer lithium ion battery negative material according to claim 2, which is characterized in that described Aliphatic small molecule selects any one of oxalic acid, succinic acid, maleic acid, fumaric acid, tartaric acid or citric acid.
4. a kind of tinbase coordination polymer lithium ion battery negative material according to claim 1, which is characterized in that described Activator selects any one of lithium hydroxide, sodium hydroxide or potassium hydroxide.
5. a kind of tinbase coordination polymer lithium ion battery negative material according to claim 1, which is characterized in that described Tin source is stannic chloride pentahydrate.
6. a kind of preparation method of tinbase coordination polymer lithium ion battery negative material according to claim 1, special Sign is that the liquid solvent is deionized water.
7. the preparation method of tinbase coordination polymer lithium ion battery negative material described in any one of claims 1-6, special Sign is, comprising the following steps:
S1, weighs activator and is dissolved in liquid solvent and form the first solution;
S2 weighs organic ligand and is dissolved in liquid solvent and mixes with the first solution, and constant temperature stirs evenly, and forms the second solution;
S3 weighs tin source and is dissolved in formation third solution in liquid solvent, third solution is added in the second solution, constant temperature adds Heat, natural cooling, centrifugation are dried to get negative electrode material is arrived.
8. the preparation method of tinbase coordination polymer lithium ion battery negative material according to claim 7, feature exist In the heating temperature of the heated at constant temperature is 110 DEG C.
9. a kind of preparation method of tinbase coordination polymer lithium ion battery negative material according to claim 7, special Sign is that the heating time of the heated at constant temperature is 24 hours.
CN201910571262.6A 2019-06-28 2019-06-28 Tin-based coordination polymer lithium ion battery cathode material and preparation method thereof Expired - Fee Related CN110408043B (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104716313A (en) * 2015-03-16 2015-06-17 哈尔滨工业大学 Preparation method for tin-based/graphene composite anode material of lithium ion battery
CN106848198A (en) * 2017-02-22 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of lithium battery cathode pole piece
CN109273715A (en) * 2018-09-21 2019-01-25 南开大学 A kind of preparation method of the coordination polymer based on 2,6- pyridinedicarboxylic acid and its application in lithium ion battery
CN109369924A (en) * 2018-09-21 2019-02-22 南开大学 A kind of synthesis of tinbase coordination polymer and its application in lithium ion battery negative material

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104716313A (en) * 2015-03-16 2015-06-17 哈尔滨工业大学 Preparation method for tin-based/graphene composite anode material of lithium ion battery
CN106848198A (en) * 2017-02-22 2017-06-13 深圳市沃特玛电池有限公司 A kind of preparation method of lithium battery cathode pole piece
CN109273715A (en) * 2018-09-21 2019-01-25 南开大学 A kind of preparation method of the coordination polymer based on 2,6- pyridinedicarboxylic acid and its application in lithium ion battery
CN109369924A (en) * 2018-09-21 2019-02-22 南开大学 A kind of synthesis of tinbase coordination polymer and its application in lithium ion battery negative material

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