CN1585160A - Preparing method for negative material of high-capacity tin-base lithium ion battery - Google Patents

Preparing method for negative material of high-capacity tin-base lithium ion battery Download PDF

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CN1585160A
CN1585160A CNA2004100091721A CN200410009172A CN1585160A CN 1585160 A CN1585160 A CN 1585160A CN A2004100091721 A CNA2004100091721 A CN A2004100091721A CN 200410009172 A CN200410009172 A CN 200410009172A CN 1585160 A CN1585160 A CN 1585160A
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CN1254873C (en
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林克芝
王晓琳
徐艳辉
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Tsinghua University
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Abstract

The producing method applies the normal temperature reactive solution SnCl2 as the solution, the ammonia as the precipitator, and the cabamide as the compound to supply the O-H, and the KBH4, NaH2PO2 as reducer. The catalyst and some compound complexing agent are also added. During the reaction procedure, the concentration of the reducer is to be controlled to keep definite ratio Sn, to reduce the irreversible capacity in the electrochemical lithium storage procedure. The material produced effectively remites the volume changing of the electrode resulted in the discharging process.

Description

A kind of preparation method of high-capacity Sn base lithium ion cell negative electrode material
Technical field
The present invention relates to a kind of preparation method of high-capacity Sn base lithium ion cell negative electrode material, especially relate to the method that a kind of preparation is applicable to the high-capacity Sn base lithium ion cell negative electrode material that various aqueous electrolyte lithium ion secondary batteries are used.Belong to the high-energy battery technical field.
Background technology
The lithium secondary battery that is utilized as portable communication apparatus and portable electric appts main power source is owing to have the focus that the excellent properties of high output voltage and high-energy-density etc. becomes domestic and international research.Yet in using the lithium secondary battery of lithium metal as negative material, separate out dendrite on the negative pole when charging, because the result of repeated charge, this dendrite can be broken through barrier film and arrive positive pole, and inside battery is short-circuited.
To this, the present negative material of lithium metal as an alternative is for can be reversibly and the material with carbon element of lithium ion reaction.Usually, lithium ion reversibly embeds and deviates from from material with carbon element and precipitating metal lithium not, does not exist because dendrite causes ground internal short-circuit problem.Yet the theoretical lithium storage content of graphitized carbon material has only 372mAh/g, is about 10% of lithium theoretical metal capacity.
In order to improve the capacity of lithium ion battery, people are carrying out can not causing the research of the negative material that Li dendrite and Capacity Ratio material with carbon element are high.Metallic tin antimony etc. can carry out reversible alloying reaction with lithium, and capacity big (990mAh/g).Tin can cause bigger change in volume when reacting with lithium ion, frequent change in volume can cause the rapid decline of electrode performance in charge and discharge process.Research thinks that the size with metallic particles is reduced to the bulk effect that sub-micron even nanoscale can reduce the Li-Sn/Sb system greatly.Some research adds not the so-called inert element with the lithium reaction in tin-based material.Report mover iron silicide (spy opens flat 5-159780 communique) is arranged, the silicide (spy opens flat 7-240201 communique) of the nonferrous metal of forming by transition metal, nickel silicide (spy opens flat 8-153517 communique), manganese silicide (spy opens flat 8-153538 communique), by containing boron group element, at least a in phosphorus and the antimony and have the CaF2 type, the material (spy opens flat 9-63651 communique) that the intermetallic compound of any crystalline texture is formed in ZnS type and the AlLiSi type; , the alloy material (spy opens flat 10-162823 communique) that forms of silicon or tin and iron or nickel; , contain at least a intermetallic compound (spy opens flat 10-223221 communique) in silicon, tin and the zinc etc.; M (1-x) Six (M=Ni, Fe, Co, Mn) (spy opens flat 10-294112 communique); MSi x(M=Ni, Fe, Co, Mn) (spy opens flat 10-302770 communique); By contain simultaneously silicon or tin etc. by the material of forming for the intermetallic compound that constitutes one of element with silicon or tin etc. that forms mutually (opening flat 11-86853 communique) as the negative material spy.European patent (disclosing communique No. 0883199) proposes to have the negative material of the solid phase B that solid solution that siliceous and tin etc. form as the solid phase A that constitutes elements and by silicon and tin etc. and other metallic elements etc. or intermetallic compound form.Propose a kind of method for preparing negative material in (CN 1317841A): with carbon class material is carrier, mix tin class or tin alloy material, incorporation is 10-50%, evenly disperse and be embedded in carrier carbon material microcosmic surface or inside, the preparation method is that the tin class organic compound with many carbon-chain structures is a presoma, is undertaken by the solid phase heating means.
Document (Journal of The Electrochemical Society, 150 (11) A1544-A1547 (2003)) provide a kind of method, the hydrogen oxide oxide S n of preparation tin in organic solution 3O 2(OH) 2, generate tin oxide SnO after the high-temperature process 2As electroactive material.This method operation is fairly simple, but adopts the organic solvent cost higher.
In sum, the Sn-containing alloy material of mentioning in most of document or the patent in theory all can not be eliminated fully owing to discharge and recharge the bulk effect that causes, and a series of problem that causes therefrom all will be the hidden danger in the battery use.Simultaneously at present the various preparation methods that contain metallic element and introduce other elements more complicated all in the patent perhaps requires than higher appointed condition, is generally high temperature solid state reaction and adopts high-energy ball milling, and relative cost is than higher.
Summary of the invention
The object of the present invention is to provide a kind of enforcement simple, normal temperature or middle temperature (20-90 ℃) reactant aqueous solution, step preparation, the preparation method of the high-capacity Sn base lithium ion cell negative electrode material that need not anneal.
The preparation method of a kind of high-capacity Sn base lithium ion cell negative electrode material that the present invention proposes is characterized in that: described method adopts normal temperature or the reaction of middle warm water solution, and reaction solution is SnCl 2The aqueous solution, precipitation reagent are ammoniacal liquor, urea, and NaOH etc. can provide the compound of hydroxide ion, and reducing agent is KBH 4, NaH 2PO 2, add reaction promoter and other compound complex agents in the solution; Product is nanometer～micron-sized Sn 3O 2(OH) 2Or Sn 6O 4(OH) 4The cluster of particle or particle, its electroactive substance is the simple substance tin through producing in the first week reduction rear electrode, its accessory substance and metallic tin are evenly distributed in the particle of nano-micrometre level one by one.This preparation method's concrete steps are:
(1) preparation A solution: at the SnCl of 0.05-0.4M 2In the aqueous solution, adding concentration is the reaction complexing agent of 0.05-2M, the 0-2M compound complex agent;
(2) preparation B solution: in concentration is the KBH of 0.05-0.8M 4Or NaH 2PO 2In one or both solution in, adding concentration is the precipitation reagent of 0.5-2M;
(3) control reaction temperature slowly is added drop-wise to solution B in the intensively stirred A solution, stirs 0.5-2 hour after waiting to dropwise again; After ageing 0-12 hour, solution is filtered, to neutral, vacuumize promptly gets product with deionised water.
In above-mentioned preparation method, the described reaction promoter of step (1) is a multi-alcohol, soap, tartaric acid, ethylenediamine tetra-acetic acid, citric acid, lactic acid, hydracrylic acid, malic acid, glycine, one or more in succinic acid complexing agent or their salt.
In above-mentioned preparation method, the described compound complex agent of step (1) is a sucrose, ethylene glycol, polyethylene glycol, one or more in the glacial acetic acid.
In above-mentioned preparation method, the described precipitation reagent of step (2) is an ammoniacal liquor, urea, NaOH, one or more in the potassium hydroxide.
Method provided by the invention can effectively be alleviated owing to repeat to discharge and recharge the electrode change in volume that causes.The ratio of Sn and O is lower than SnO in this material simultaneously 2In ratio, can reduce the irreversible capacity that first week discharged and recharged to a certain extent.The negative material capacity of producing according to this method is greater than the theoretical capacity of material with carbon element usually, and charge and discharge platform is higher than the voltage that Li dendrite is separated out at 0.2-0.7V, and the high current charge-discharge ability is higher than common material with carbon element.
When implementing this method, also can make to have a certain proportion of simple substance tin in the product by regulating the concentration of reducing agent, the irreversible capacity in first week further reduces when making this material as lithium ion battery negative.
Description of drawings
Fig. 1 is the circulation volume curve of the sample in the embodiment of the invention 3.
Fig. 2 is the x-ray diffraction pattern (Sn of sample in the embodiment of the invention 1 3O 2(OH) 2).
Embodiment
Below in conjunction with embodiment technical scheme of the present invention is described further:
Preparation A solution: the SnCl of 0.05-0.4M 2In the aqueous solution, add reaction promoter (multi-alcohol, soap, tartaric acid, ethylenediamine tetra-acetic acid, citric acid, lactic acid, malic acid, glycine, in complexing agents such as succinic acid or their salt one or more, hydracrylic acid-lactic acid), concentration is 0.05-2M, compound complex agent (sucrose, wherein one or more of ethylene glycol, polyethylene glycol, glacial acetic acid etc.) (0-2M);
Preparation B solution: KBH 4Or NaH 2PO 2(wherein one or more) are solution (0.05-0.8M), wherein adds precipitation reagent (ammoniacal liquor, urea, NaOH etc. wherein one or more), and concentration is 0.5-2M.
Control reaction temperature slowly is added drop-wise to solution B in the intensively stirred A solution, stirs 0.5-2 hour after waiting to dropwise again.After ageing 0-12 hour, solution is filtered, to neutral, vacuumize promptly gets product with deionised water.
The product that obtains is made electrode.The preparation of electrode: the carbon dust that 10mg was handled places small beaker, the weight ratio of pressing 5-15% adds acetylene black, the weight ratio of pressing 5-15% adds 10% polytetrafluoroethylene aqueous emulsion, adds absolute ethyl alcohol 5-20ml again, puts into the ultrasonic dispersion of ultrasonic cleaning machine 5-30 minute.The sample that disperses is applied to (nickel foam, stainless (steel) wire, copper mesh, nickel screen, Copper Foil etc.) on the collector body in 90 ℃ of heating breakdown of emulsion oven dry in 5-30 minute with slurry, and dry 1 hour, 20MPa compacting 10 minutes, 120 ℃ of vacuumizes were more than 12 hours, and sealing is preserved standby.
Battery assembling: as to electrode and reference electrode, electrolyte is selected ethylene carbonate (EC) for use: dimethyl carbonate (DMC)=1: 1 (volume ratio) is as the LiPF of solvent with the lithium sheet 6Solution, equipment glass three-electrode battery leaves standstill laggard column electrode performance test in 30-60 minute.
Adopt constant current charge-discharge, current density is 40mA/g, discharges and recharges between 0-1.2V to carry out.
Embodiment 1
Preparation A solution: the SnCl of 0.07M 2Solution 50ml wherein adds sodium potassium tartrate tetrahydrate, and concentration is 0.2M, sucrose, and concentration is 0.01M; Preparation B solution: the KBH of 0.1M 4Solution 30ml adds ammoniacal liquor, and ammonia concentration is 2M.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 2 hours, temperature is 25 ℃ in this process.Reaction solution ageing 1 hour, the white precipitate that produces filtered and with deionized water wash to neutral, obtain product after 90 ℃ of dryings.Carry out electrochemical property test by the system method power backup utmost point noted earlier.
Embodiment 2
Preparation A solution: the SnCl of 0.07M 2Solution 50ml wherein adds natrium citricum, and concentration is 0.2M, adds ethylene glycol 2ml; Preparation B solution: the KBH of 0.1M 4Solution 30ml wherein adds urea, and concentration is 0.4M.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 2 hours, temperature is 65 ℃ in this process.Reaction solution ageing 3 hours, the white precipitate that produces filtered and with deionized water wash to neutral, obtain product after 90 ℃ of dryings.Prepare electrode by method noted earlier and carry out electrochemical property test.
Embodiment 3
Preparation A: the SnCl of solution 0.06M 2Solution 50ml wherein adds tartaric acid, and concentration is 0.2M, adds ethylene glycol 1ml; Preparation B solution: the KBH of 0.07M 4Solution 30ml wherein adds ammoniacal liquor, and ammonia concentration is 1M.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 1.5 hours, temperature is 45 ℃ in this process.Reaction solution ageing 10 hours, the white precipitate of generation are filtered and are extremely neutral with deionized water wash, obtain product after 90 ℃ of dryings.Prepare electrode by method noted earlier and carry out electrochemical property test.
Embodiment 4
Preparation A solution: the SnCl of 0.1M 2Solution 50ml wherein adds natrium citricum, and concentration is 0.4M, adds polyethylene glycol, and concentration is 0.05M; Preparation B solution: the KBH of 0.2M 4Solution 30ml wherein adds ammoniacal liquor, and ammonia concentration is 1.5M in the solution.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 1.5 hours, temperature is for being controlled to be 75 ℃ in this process.The white precipitate that produces filters and is extremely neutral with deionized water wash, obtains product after 90 ℃ of dryings.Carry out electrochemical property test by preparation electrode noted earlier.
Embodiment 5
Preparation A solution: the SnCl of 0.08M 2Solution 50ml wherein adds sodium lactate, and concentration is 0.3M; Preparation B solution: the KBH of 0.1M 4Solution 30ml wherein adds ammoniacal liquor, and ammonia concentration is 1M.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 1.5 hours, temperature is controlled to be 45 ℃ in this process.Reaction solution ageing 6 hours, the white precipitate of generation are filtered and are extremely neutral with deionized water wash, obtain product after 90 ℃ of dryings.Prepare electrode by method noted earlier and carry out electrochemical property test.
Embodiment 6
Preparation A solution: the SnCl of 0.08M 2Solution 50ml wherein adds sodium potassium tartrate tetrahydrate, and concentration is 0.3M, adds ethylene glycol, and concentration is 0.05M; Preparation B solution: the KBH of 0.07M 4Solution 30ml wherein adds NaOH, and concentration is 0.2M.B solution slowly is added drop-wise among the A, simultaneously strong agitation A solution.After waiting to dropwise, continue to stir 1 hour, temperature is 55 ℃ in this process.The white precipitate that produces filters and is extremely neutral with deionized water wash, obtains product after 90 ℃ of dryings.Prepare electrode by method noted earlier and carry out electrochemical property test.
Embodiment 7:
With 380 ℃ of annealing of the product among the embodiment 15 hours, products therefrom was prepared into electrode and carries out the electrochemistry capacitance test.
Embodiment 8:
With 350 ℃ of annealing of the product among the embodiment 3 12 hours, products therefrom was prepared into electrode and carries out the electrochemistry capacitance test.
Table 1
The embodiment numbering Particle mean size (μ m) The chemical property of corresponding simulated battery
Reversible capacity (mAh/g) (first week) Cycle performance parameter % (second week/the first week) Reversible capacity (the tenth week) The capacity attenuation rate
1 1-2 680 0.96 536 2.1％
2 0.5-0.9 696 0.925 520 2.5％
3 1.1-1.7 680 1.088 672 0.11％
4 0.1-0.4 632 0.962 416 3.4％
5 0.3-0.6 612 0.932 456 2.5％
6 0.2-0.5 645 0.658 464 2.8％
7 1-1.5 633 0.816 406 3.65
8 0.8-1.4 624 0.876 486 2.2％

Claims (4)

1, a kind of preparation method of high-capacity Sn base lithium ion cell negative electrode material is characterized in that: described method adopts normal temperature or the reaction of middle warm water solution; Reaction solution is SnCl 2The aqueous solution, precipitation reagent are ammoniacal liquor, urea, and NaOH etc. can provide the compound of hydroxide ion, and reducing agent is KBH 4, NaH 2PO 2, add the reaction complexing agent in the solution, other auxiliary agents; Product is nanometer～micron-sized Sn 3O 2(OH) 2Or Sn 6O (OH) 4The cluster of particle or particle, its electroactive substance is simple substance tin through producing in first all electrochemical reduction rear electrodes, its accessory substance and metallic tin are evenly distributed on one by one in nanometer～micron-sized particle; Also can make and contain a certain proportion of metallic tin in the product by the concentration of reducing agent in the control reaction solution.This preparation method's concrete steps are:
(1) preparation A solution: at the SnCl of 0.05-0.4M 2In the aqueous solution, adding concentration is the reaction promoter of 0.05-2.5M, the 0-2.5M compound complex agent;
(2) preparation B solution: in concentration is the KBH of 0.05-0.8M 4Or NaH 2PO 2In one or both solution in, adding concentration is the precipitation reagent of 0.05-3M.
(3) control reaction temperature slowly is added drop-wise to solution B in the intensively stirred A solution, and the control pH value is between 8-14; Stirred again after waiting to dropwise 0.5-2 hour; After ageing 0-12 hour, solution is filtered, to neutral, vacuumize promptly gets product with deionised water.
2, according to the described preparation method of claim 1, it is characterized in that: the described reaction promoter of step (1) is a multi-alcohol, soap, tartaric acid, ethylenediamine tetra-acetic acid, citric acid, lactic acid, hydracrylic acid, malic acid, glycine, one or more in succinic acid complexing agent or their salt.
3, according to the described preparation method of claim 1, it is characterized in that: the described compound complex agent of step (1) is a sucrose, ethylene glycol, polyethylene glycol, one or more in the glacial acetic acid.
4, according to the described preparation method of claim 1, it is characterized in that: the described precipitation reagent of step (2) is an ammoniacal liquor, urea, one or more in the NaOH etc.
CNB2004100091721A 2004-06-03 2004-06-03 Preparing method for negative material of high-capacity tin-base lithium ion battery Expired - Fee Related CN1254873C (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100386905C (en) * 2006-05-26 2008-05-07 清华大学 Metal particle-cladded active carbon microsphere cathode composite materials and method for preparing same
CN100446309C (en) * 2007-05-23 2008-12-24 福建师范大学 Preparation method for controlling grain size of cathode material of tin - copper - nickel - cobalt alloy
CN101423253B (en) * 2008-11-26 2010-06-16 华中师范大学 ZnV2O4 lithium storage materials and preparation method thereof
CN102208605A (en) * 2011-04-25 2011-10-05 长安大学 Method for preparing tin-carbon nano composite electrode material
CN103178248A (en) * 2013-04-18 2013-06-26 厦门大学 Preparation method of tin-cobalt alloy cathode material of lithium ion battery
CN103367741A (en) * 2012-03-26 2013-10-23 比亚迪股份有限公司 Negative electrode active material and preparation method thereof, as well as lithium ion battery
CN110071268A (en) * 2019-03-25 2019-07-30 天津大学 Preparation is used for method of four phosphatizations, the three tin rivet in carbon skeleton composite material of sodium ion negative electrode material

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100386905C (en) * 2006-05-26 2008-05-07 清华大学 Metal particle-cladded active carbon microsphere cathode composite materials and method for preparing same
CN100446309C (en) * 2007-05-23 2008-12-24 福建师范大学 Preparation method for controlling grain size of cathode material of tin - copper - nickel - cobalt alloy
CN101423253B (en) * 2008-11-26 2010-06-16 华中师范大学 ZnV2O4 lithium storage materials and preparation method thereof
CN102208605A (en) * 2011-04-25 2011-10-05 长安大学 Method for preparing tin-carbon nano composite electrode material
CN102208605B (en) * 2011-04-25 2013-09-25 长安大学 Method for preparing tin-carbon nano composite electrode material
CN103367741A (en) * 2012-03-26 2013-10-23 比亚迪股份有限公司 Negative electrode active material and preparation method thereof, as well as lithium ion battery
CN103367741B (en) * 2012-03-26 2016-04-27 比亚迪股份有限公司 A kind of negative active core-shell material and preparation method thereof and a kind of lithium ion battery
CN103178248A (en) * 2013-04-18 2013-06-26 厦门大学 Preparation method of tin-cobalt alloy cathode material of lithium ion battery
CN103178248B (en) * 2013-04-18 2015-08-05 厦门大学 The preparation method of tin-cobalt alloy cathode material of lithium ion battery
CN110071268A (en) * 2019-03-25 2019-07-30 天津大学 Preparation is used for method of four phosphatizations, the three tin rivet in carbon skeleton composite material of sodium ion negative electrode material
CN110071268B (en) * 2019-03-25 2021-11-23 天津大学 Method for preparing tri-tin tetraphosphorylation rivet-on-carbon framework composite material for sodium ion negative electrode material

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