CN1142607C - Composite C-base alloy electrode material for lithium ion battery and its preparing process - Google Patents
Composite C-base alloy electrode material for lithium ion battery and its preparing process Download PDFInfo
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- CN1142607C CN1142607C CNB011130601A CN01113060A CN1142607C CN 1142607 C CN1142607 C CN 1142607C CN B011130601 A CNB011130601 A CN B011130601A CN 01113060 A CN01113060 A CN 01113060A CN 1142607 C CN1142607 C CN 1142607C
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- 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 relates to a carbon-base alloy composite electrode material for negative electrodes of lithium ion batteries and a preparing method thereof, which belongs to the field of lithium batteries. The carbon-base alloy composite electrode material of the present invention is characterized in that negative electrode materials take carbon type materials as a carrier, and the carbon type materials are doped with 10 wt% to 50 wt% of tin type or tin and lithium alloy materials evenly dispersed on the microscopic surface of the carbon materials of the carrier or in the carbon materials of the carrier. The preparing method of the present invention has the steps that a tin type organic compound with a multiple carbon chain structure is used as a predecessor object, and the materials are treated by solid-phase heating. The carbon-base alloy composite electrode material of the present invention has the characteristics of low price and rich varieties, and is suitable for large-scale industrialized production.
Description
The invention relates to a preparation method of a novel carbon-based alloy composite electrode material for a negative electrode in a lithium ion battery, in particular to a carbon-based alloy composite negative electrode material with high specific capacity and long cycle life and a preparation method thereof, belonging to the field of lithium batteries.
With the rapid development of the microelectronic industry and information technology and the wide application of various portable communication devices, personal computers, cameras, small electronic devices, etc., batteries with high specific energy, light weight and capable of being charged and discharged for many times become an urgent need. Moreover, environmental protection and the worldwide energy crisis also put more recent demands on the development of batteries. Lithium ion batteries were produced in this context and were first proposed and produced by the japanese sony corporation in the early 90 s. Different from the traditional lithium battery, the lithium ion battery is a breakthrough of a negative electrode material in the battery, the graphite carbon material is used as a lithium storage source, and the charge-discharge reaction of the battery can be regarded as Li+The lithium ion battery is called a lithium ion battery because of the insertion and the detachment between the positive electrode and the negative electrode, and is also called a rocking chair type battery, and the charging and discharging processes of the lithium ion battery are as follows: . The lithium ion battery is actually a lithium ion concentration battery, and the positive electrode and the negative electrode are composed of two different lithium ion intercalation compounds. During charging, lithium ions are extracted from the positive electrode and are inserted into the negative electrode through electrolysis, the positive electrode is in a lithium-poor state, the negative electrode is in a lithium-rich state, working voltage is formed, and the opposite is achieved during discharging.
Compared with other secondary batteries appearing in the current market, such as lead-acid batteries, nickel-cadmium batteries, nickel-hydrogen batteries and the like, the lithium ion batteries have the prominent main advantages that: high energy density (>100 wh/kg); long service life (cycle times are more than 1000); no memory effect; high operating voltage (around 3.6V); green power supply (no pollution to environment).
The cathode material widely used in the production of the lithium ion battery at present is graphite material, and Li is embedded into the cathode of the graphite structure to form LiC-like material6When the battery is in a fully charged state, the negative electrode is close to the electrode potential of the metal lithium, which is beneficial to maintaining the lithiumThe higher potential of the ion battery. The graphite carbon material has a soft structure and good performance of reversible lithium intercalation and deintercalation, but the capacity of the material is relatively limited, and the theoretical capacity is 372 mAh/g.
The search for high energy density negative electrode materials other than carbon materials has been the hot spot in lithium ion battery research, and at present, one research hot spot in this field is to use metals such as Al, Sn, Pb, Si, Sb, etc. capable of alloying with Li, and the quantity of reversible insertion and extraction Li of these lithium storage metal materials is fargreater than that of graphite, such as Li4.4The charge density of Sn is 978mAh/g, but the graphite cathode cannot be replaced in the lithium ion battery at present, and the main reason is that the Li-Me alloy system undergoes several phase changes during Li intercalation and deintercalation, so that the material is seriously expanded and contracted in volume, and the serious volume effect can cause the fission of the material, so that a series of performance changes of the cathode are caused, such as the reduction of the cycling stability and the like. Research suggests that reducing the size of metal particles to submicron, even nanometer levels can greatly reduce the severe volume efficiency of Li-Me systemsShould be used. Although the method for preparing the composite oxide system by taking amorphous SnO as a precursor proposed by Nippon Fuji corporation can greatly reduce the volume effect of the Li-Me negative electrode and improve the cycle performance of the negative electrode material, the material prepared by the method has high first irreversible capacity caused by the use of the material because SnO generates Li in the alloying process2O is irreversible, so that the first charge-discharge efficiency is very low, and the application of the material in practice is seriously influenced. In addition, the method for improving the cycle performance of the Li-Me system can adopt an alloy system structure MM', such as Sn-Sb, Sn-Cu and the like, and the material with the structure can inhibit the volume effect caused by lithium intercalation or deintercalation. However, the cycle performance of the materials of the structure is still to be further improved.
Because the graphite carbon material has a certain specific capacity, has better elasticity and weak lithium insertion volume expansion effect (about 9%), if the high-capacity lithium storage metal is highly dispersed and fixed on the surface or inside the carbon-based material toform the metal-carbon composite negative electrode material, the whole volume change effect of the electrode in the charging and discharging process is expected to be greatly reduced, thereby improving the mechanical and electrical conductivity of the electrode, and finally effectively improving the reversible capacity and the cycling stability of the electrode. The studies on this aspect have not yet achieved very satisfactory results and have remained in the preliminary laboratory exploration phase.
The invention aims to provide a carbon-based alloy composite electrode material used as a lithium ion battery cathode and a preparation method thereof, so as to improve the energy density of the lithium ion battery cathode material and enable the cathode material to have better charge and discharge characteristics than the carbon-based cathode material commonly used in the lithium ion battery in the current commercial market.
The invention is realized in such a way that the novel lithium ion battery cathode material is characterized by comprising the following components in parts by weight:
(1) carbon material with certain lithium storage capacity and cycle life is used as a carrier of the composite material;
(2) the high-capacity tin or tin and lithium storage alloy material is a doped material of the composite material, the electrochemical performance of the composite material, such as specific capacity, cycle performance and the like, is highly dependent on the content of the doped material, and the content of the doped material can be generally 10-50% according to the microstructure, specific surface area and the like of a carrier material;
(3) the grain size of the microcosmic tin-plating and lithium-storing alloy doping material is submicron or near nanometer, and the microcosmic tin-plating and lithium-storing alloy doping material is highly and uniformly dispersed and embedded on the microcosmic surface or inside of the carrier carbon material;
(4) the composite material has the advantages of the carbon material and the alloy material, namely the high reversible capacity of the alloy material and the long cycle life of the carbon material;
(5) the charge-discharge characteristics of the composite material are the charge-discharge characteristics of the carrier carbon material and the alloy doped material, and the composite characteristics.
The novel high-capacity carbon-based alloy composite cathode in the lithium ion battery is prepared by taking a tin organic compound with a polysulfide chain structure as a precursor through a solid phase heating method, and the preparation method comprises the following specific steps:
(1) dissolving tin organic compound with multi-carbon chain structure in organic solvent, and slowly stirring to make it uniformly dissolved;
(2) a metal capable of forming a lithium-storing alloy with tin, a precursor for its preparation, i.e., a metal oxide, or a metal organic compound, is slowly added to the solution formed in (1);
(3) slowly adding the carbon carrier material into the solution formed in the step (2) which is uniformly mixed, uniformly treating, and simultaneously carrying out heat treatment;
(4) after the organic solvent is primarily volatilized, heating the mixture in an aggregation state to a certain temperature, and completely removing the organic solvent in the solution;
(5) the mixture is moved into a sealing system, a specified atmosphere (containing a certain amount of reducing gas and the rest inert gas) is introduced into the sealing system, thesealing system is placed in a heating device, the temperature is suddenly raised to a certain temperature, and the reaction time is controlled;
(6) and (3) after the reaction time is over, suddenly reducing the reaction temperature in the sealed system, and rapidly cooling to room temperature, wherein reactants are always in the specified atmosphere protection in the whole process.
The tin organic compound with a multi-carbon chain structure can be one or a mixture of more than one of a plurality of tin organic compounds such as 2-ethyl tin hexanoate, 2-ethylhexyl dimethyl tin, dibutyltin maleate, dibutyltin dilaurate, dibutyltin monobutylate, tin dimaleate, monoethyl dioctyltin dimaleate or monoisooctyl dioctyltin dimaleate;
the organic solvent can be any organic solvent which has certain volatility and has the dissolving capacity of organic compounds and is commonly used in industry, such as acetone, ethanol, tetrahydrofuran, pyrrole, pyridine, benzene and the like;
the metal capable of forming lithium storage alloy with tin, such as Sb, Cu, Pb, Mg, In, Ag, Ni, and the like, and the preparation precursor of the metal can be oxide or metal organic compound, metal inorganic compound, and the like of the metal;
the carbon carrier material is any one of carbon materials commonly used in the production of lithium ion batteries in commerce at present, and can be coke, mesocarbon microbeads, artificial graphite, natural graphite, porous carbon and the like; the content of the carrier in the composite electrode material is 50-90 wt%.
The heating to a certain temperature can be 60-100 ℃;
the reaction temperature can be 450-700 ℃;
the defined reaction atmosphere may be any reducing gas, such as H2CO, etc. with a content of about 4-6 Vol%,and the balance of inert gases (Ar, He, N)2Etc.);
the sealing system can be a plurality of sealing systems with air inlet and outlet devices, which can ensure that the interior of the sealing system has specified atmosphere protection;
the sudden temperature rise and the rapid cooling after the reaction are the key points in the whole solid-phase reaction, wherein the sudden temperature rise and the rapid cooling can be realized by controlling a temperature program controller of a heating furnace, or can be realized by rapidly moving a sealed reaction device into/out of the heating furnace with a fixed temperature range, wherein the temperature rise rate is more than 200 ℃/min, and the temperature drop rate is more than 100 ℃/min;
the reaction time is started when the reaction temperature in the sealing device reaches the reaction specified temperature and is started before the reaction temperature suddenly drops, and the reaction time can be differentiated according to different reactant quantities and different reactant structures and can be 10-80 minutes;
the invention uses a tin organic compound with low price and rich variety of multi-carbon chain structure as a composite material to prepare a precursor, the carrier material is a carbon cathode material widely used in the production of the lithium ion battery at present, the preparation method is an industrially implementable solid phase heating method, and the preparation method is an industrially implementable solid phase heating method and is suitable for industrial mass production. The prepared composite negative electrode material has the specific capacity greatly higher than that of the carbon negative electrode material commonly used in the lithium ion battery at present, has the cycle life greatly longer than that of the alloy negative electrode material with the high specific capacity at present, can be widely applied to the production of the lithium ion battery, and greatly improves the performance of the battery.
The invention discloses a carbon-based alloy composite electrode material used as a lithium ion battery cathode and a preparation method thereof, which are briefly described by taking five examples.
Example 1
Preparing the pure tin composite negative electrode material taking the mesocarbon microbeads (MCMB) as the carrier. 2-ethylhexyl dimethyl tin with a certain proportion (the content of tin in the composite material is 22wt percent after the reaction is finished) is dissolved in a pyridine organic solvent and slowly and uniformly mixed; slowly adding a certain proportion of mesophase carbon microsphere powder (the content of the mesophase carbon microsphere in the composite material is 78 wt% after the reaction is finished), uniformly treating and simultaneously heating, removing the organic solvent, and keeping the temperature above 60 ℃; the dried Sn/MCMB mixture is transferred into a sealing device and is protected by introducing mixed gas (4.9 percent H)2And Ar) in the rest, moving the sealing device into a heating furnace, and suddenly heating to more than 450 ℃, wherein the heating rate is more than 200 ℃/min, and the reaction time is about 20 min. And (4) quickly moving the sealing device out of the heating furnace, rapidly cooling at room temperature, and always protecting by a specified atmosphere in the whole process. The mixture after reaction is made into an electrode plate, and the electrode plate and the metal Li are made into a button cell. The current density of charge and discharge is tested to be 0.2mA/cm2And the cut-off charge-discharge voltage is 0V-1.5V.
Example 2
Preparing the tin-antimony alloy composite negative electrode material taking coke as a carrier. Dissolving dibutyl tin maleate (wherein Sn: Sb, 1: 1, molar ratio) in pyrrole organic solvent at a certain proportion, slowly mixing uniformly, and adding Sb2O3(wherein Sn: Sb, 1: 1, molar ratio, 31 wt% of tin-antimony alloy in the composite material after the reaction is finished), and a certain proportion of coke powder (69 wt% of coke powder in the composite material after the reaction is finished) are slowly added in sequence, and the subsequent preparation steps are the same as those in example 1.
Example 3
Preparing the tin-copper alloy composite negative electrode material taking the artificial graphite as a carrier. Dissolving a certain proportion of 2-ethyl tin hexanoate and 2-ethyl copper hexanoate salt (the molar ratio of Sn to Cu is 5: 6, and the content of tin-copper alloy in the composite material after the reaction is finished is 43 wt%) in a tetrahydrofuran organic solvent, and slowly and uniformly mixing; a certain proportion of artificial graphite material (57 wt% of artificial graphite in the composite material after the reaction) was slowly added, followed by the same preparation procedure as in example 1.
Example 4
Preparing the tin-nickel alloy composite cathode material with porous carbon as a carrier. Dibutyl tin dilaurate with a certain proportion (wherein Sn: Ni, 1: 1, molar ratio, the content of tin-nickel alloy in the composite material after the reaction is finished is 38 wt%) is slowly dissolved in an acetone organic solvent, the mixture is uniformly mixed, nickel oxide with a certain proportion (Sn: Ni, 1: 1, molar ratio) is slowly added, porous carbon with a certain proportion (the content of the porous carbon in the composite material after the reaction is finished) is simply thermally treated, then ultrasonic mixing is carried out, and the preparation steps are the same as those in example 1.
Example 5
Preparing the tin-silver alloy composite negative electrode material taking natural graphite as a carrier. Mono-isooctyl dimaleate dioctyl tin (wherein Sn: Ag, 1: 2, molar ratio, content of tin-silver alloy in the composite material after reaction is 35 wt%) in a certain proportion is dissolved in an ethanol organic solvent, the mixture is heated and mixed uniformly, silver carbonate (wherein Sn: Ag, 1: 2, molar ratio) in a certain proportion is slowly added, the mixture is mixed uniformly, and the preparation steps are the same as those in example 1 after a certain proportion of porous carbon (according to content of natural graphite in the composite material after reaction is finished).
The specific capacity of the novel high-capacity carbon-based alloy composite negative electrode material prepared by the embodiment is obviously higher than that of a carbon negative electrode material commonly used in the production of the lithium ion battery at present, for example, the tin composite negative electrode material prepared in the embodiment 1 and using the mesocarbon microbeads as carriers has the reversible specific capacity of 400mAh/g, the specific capacity is improved by about 25% compared with that of the mesocarbon microbead carrier material (the reversible specific capacity of the general mesocarbon microbead negative electrode material is about 310 mAh/g), the first charge-discharge efficiency is more than 80%, and the capacity is hardly attenuated after more than 60 times of circulation; in addition, the specific capacities of the tin-antimony alloy composite negative electrode material using coke as a carrier and the tin-copper alloy composite negative electrode material using artificial graphite as a carrier prepared in the embodiments 2 and 3 are respectively improved to different degrees (10% -40% relative to the carrier material) comparedwith the carrier material, and the cycle life is much longer than that of the alloy negative electrode material and is close to the long cycle life of the carbon material. Because the invention uses a tin organic compound with low price and rich varieties and multi-carbon chain structure as the precursor for preparing the composite material, the preparation method is an industrially implementable solid phase heating method and is suitable for industrial mass production.
Claims (7)
1. A preparation method of a carbon-based alloy composite electrode material used as a lithium ion battery cathode is characterized in that a tin organic compound with a multi-carbon chain structure is used as a precursor, and the carbon-based alloy composite electrode material is prepared by a solid phase heating method, and comprises the following specific steps:
(1) dissolving tin organic compound with multi-carbon chain structure in organic solvent, and slowly stirring to make it uniformly dissolved;
(2) preparing a precursor, namely a metal oxide or a metal organic compound, from a metal capable of forming a lithium-storage alloy in tin, and slowly adding the precursor into the solution;
(3) slowly adding the carbon carrier material into the uniformly mixed solution, uniformly treating, and simultaneously carrying out heat treatment;
(4) after the organic solvent is primarily volatilized, heating the mixture in an aggregation state to a certain temperature, and completely removing the organic solvent in the solution;
(5) the mixture is transferred into a sealed system, and H with 4-6 vol% is introduced into the system2Or Ar, He, N of CO reducing gas2The protective atmosphere, the sealing body is arranged in the heating device, and the reaction time is controlled after the temperature is suddenly raised to 450-700 ℃;
(6) and (4) after the reaction time is over, suddenly reducing the reaction temperature in the sealed system, and rapidly cooling to room temperature.
2. The method according to claim 1, wherein the tin-based organic compound having a multi-carbon chain structure is one or more of tin 2-ethylhexanoate, dimethyl tin 2-ethylhexyl ester, dibutyl tin maleate, dibutyl tin dilaurate, dibutyl tin monobutyl maleate, dioctyl tin dimaleate, and diisooctyl tin dimaleate.
3. The method for preparing a carbon-based alloy composite electrode material used as a negative electrode of a lithium ion battery according to claim 1, wherein the organic solvent is one of acetone, ethanol, tetrahydrofuran, pyrrole and pyridine.
4. The method of claim 1, wherein the metal capable of forming a lithium-storing alloy with tin is one of Sb, Cu, Pb, Mg, In, Ag, or Ni; the precursor is an oxide of the metal or a metal organic compound or a metal inorganic compound.
5. The method for preparing the carbon-based alloy composite electrode material as the negative electrode of the lithium ion battery according to claim 1, wherein the carbon-based carrier material is coke, mesocarbon microbeads, artificial graphite, natural graphite or porous carbon; the content of the carrier in the composite electrode material is 50-90 wt%.
6. The method for preparing the carbon-based alloy composite electrode material used as the negative electrode of the lithium ion battery according to claim 1, wherein the reaction time is 10-80 minutes.
7. The method for preparing a carbon-based alloy composite electrode material used as a negative electrode of a lithium ion battery according to claim 1, wherein the temperature is suddenly increased at a rate of more than 200 ℃/min, and the temperature is rapidly decreased at a rate of more than 100 ℃/min after the reaction.
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| CN100386906C (en) * | 2006-05-26 | 2008-05-07 | 清华大学 | Active-carbon-microball coated metal composition negative polar material and preparing method |
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