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 PDFInfo
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- 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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- 239000013256 coordination polymer Substances 0.000 title claims abstract description 36
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 36
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 13
- 239000013110 organic ligand Substances 0.000 claims abstract description 11
- 239000012190 activator Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000007773 negative electrode material Substances 0.000 claims description 11
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical group Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 claims description 5
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 4
- -1 aliphatic small molecule Chemical class 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 239000001530 fumaric acid Substances 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 2
- 239000011976 maleic acid Substances 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims 1
- 239000011975 tartaric acid Substances 0.000 claims 1
- 235000002906 tartaric acid Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- 239000010406 cathode material Substances 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000007825 activation reagent Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 238000009938 salting Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 21
- 239000011259 mixed solution Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 229960000935 dehydrated alcohol Drugs 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 239000001384 succinic acid Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000004087 circulation Effects 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910001432 tin ion Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
- H01M4/602—Polymers
- H01M4/604—Polymers containing aliphatic main chain polymers
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
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
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.
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Citations (4)
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 |
-
2019
- 2019-06-28 CN CN201910571262.6A patent/CN110408043B/en not_active Expired - Fee Related
Patent Citations (4)
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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