CN100438149C - Method for preparing high capacity lithium ion cells cathode material - Google Patents
Method for preparing high capacity lithium ion cells cathode material Download PDFInfo
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- CN100438149C CN100438149C CNB200610012111XA CN200610012111A CN100438149C CN 100438149 C CN100438149 C CN 100438149C CN B200610012111X A CNB200610012111X A CN B200610012111XA CN 200610012111 A CN200610012111 A CN 200610012111A CN 100438149 C CN100438149 C CN 100438149C
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/10—Energy storage using batteries
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a submicron powder alloy particles and its utilization, and is is in order to provide a cathode material for lithium battery. It comprises following steps: arc heating and melting metals with inert gas such as argon to get alloy, then under condition of with the mixture gas of hydrogen and inert gas, evaporating alloy to submicron powder by controlling arc current, arc pressure and total pressure, inactivating and getting material that can be used as cathode materials for lithium battery. The invention is characterized in that the reversible stored kalium of prepared submicron powder is 2-3 times as much as that of general carbon material generally used in current days, and the circularity is good.
Description
Technical field
The present invention relates to a kind of preparation method of cathode material for high capacity lithium ion battery, belong to technical field of lithium ion.
Background technology
The secondary cell of the novel green that lithium ion battery is wide as a kind of high voltage, high-energy-density, lightness, serviceability temperature, have extended cycle life, security performance is good, be widely used in each electronic product at present, as portable sets such as notebook computer, mobile phones, electric automobile, electrical energy storage, the aerospace satellite, miniature electronic device or the like.
At present, the negative material that is used to lithium ion battery mainly is various material with carbon elements such as petroleum coke, carbon fiber, RESEARCH OF PYROCARBON, native graphite, Delanium, and its major advantage is its efficiency for charge-discharge height, have good cycle life.But the theoretical specific capacity of material with carbon element has only 372mAh/g, and actual capacity is lower, can not satisfy the further demand of people to high-capacity battery.The non-carbon negative pole material of many novel alloy type is suggested, as Sn, Sb, Al, Si, Ag etc. can with Li alloyed metal (AM) and alloy thereof, their reversible lithium storage capacity is all much larger than the graphite-like negative material.But the subject matter of alloy type negative material is very easily efflorescence in the repeated charge process, thereby adds the contact resistance between the bulky grain, causes the cycle life of electrode on the low side.A kind of way is to adopt superfine alloy and activity/nonactive composite alloy system, and the absolute volume of each particle of superfine alloy in charge and discharge process changes less, and non-active material plays the effect of dispersion, buffer medium.Should have good cyclicity and less capacitance loss as lithium ion battery negative material.SnSb alloy for example is because alloying reaction (Li can both take place with Li in two kinds of elements of Sn and Sb
22Sn
5: 994mAh/g, Li
3Sb:660mAh/g), the high theoretical capacity being arranged, shown electrochemical behavior preferably, is a kind of kamash alloy class negative material likely, is subject to people's attention.But, different preparation methods the alloy material performance difference that arrives very big.The preparation method of present SnSb alloy mainly contains methods such as solwution method, solid reaction process and prepares the SnSb alloy.Solwution method generally is to use NaBH
4Or the Zn powder is that the chloride of reducing agent reducing metal salt in the aqueous solution or organic solvent obtains alloy.Although this method can prepare short grained SnSb alloyed powder, but, often there are remaining boron element, chloride ion or hydroxide ion in the surface of SnSb alloyed powder, be difficult to remove clean, electrochemical behavior to electrode can produce certain influence, preparation technology is difficult to control, and synthetic cost is higher.The solid reaction process preparation method is easy, and cost is low, but the powder particle size that obtains is bigger, and cycle performance is very undesirable.
Summary of the invention
The purpose of this invention is to provide a kind of ultra micro powder particles and preparation method thereof that is suitable for as lithium ion battery alloy class negative material.
Ultra micro powder particles provided by the present invention is that granularity is the alloying pellet of 1nm to 1000nm, and preferred 1nm is to 300nm.The preferred SnSb of described alloy ultra micro powder particles, SnFe, SnNi, SiNi or SiFe etc. wherein most preferably are SnSb.
Preparing above-mentioned alloy ultra micro powder particles may further comprise the steps:
(1) smelt stage: each component (being generally two kinds of components) that desire is prepared alloy is in predetermined ratio batching, in inert atmosphere, obtain alloy pig with the arc heating melting, for each component is mixed, alloy pig will spin upside down and carry out repeatedly melting several times.
Usually alloy compositions is placed on the water-cooling subbase in the reaction cavity (reaction chamber of hydrogen arc-plasma preparation facilities as shown in Figure 1) of a sealing (being generally copper coin), in inert atmospheres such as argon gas, obtains alloy pig with the arc heating melting.
(2) the powder process stage: after smelt stage is finished, inert gas is taken out a part, feed a certain amount of hydrogen then, control arc current, arc voltage and atmosphere total pressure etc. make alloy begin a large amount of evaporations and generation ultra micro powder particles.
The content of above-mentioned hydrogen is 0～100%, general≤50%; The value of electric current is 50～1000A, is generally 100～300A; Magnitude of voltage is＜safe voltage of 36V, be generally 20～25V; The atmosphere total pressure generally is no more than 0.1Mpa.
(3) the passivation stage: will carry out Passivation Treatment to the ultra micro powder particles after powder process is finished, to prevent its spontaneous combustion in air.
Passivation is meant under the condition of a gentleness, make the surface of metal particles that obtains form the very thin oxide layer of one deck, oxidized thereby no longer continue the inside of protection particle, conventional method is to vacuumize after preparation is finished, in cavity, feed very a spot of air again, keep a few hours; Or after preparation finishes, in cavity, feed the mixed atmosphere of very a spot of air and gases such as argon gas or nitrogen, wherein the content of air generally is controlled at below 10%, maintenance a few hours.
(4) collection phase: will collect with standby through the ultra micro powder particles of Passivation Treatment.
Can collect the ultra micro powder particles by centrifugal collector or filtering type gatherer.
When preparation alloy ultra micro powder particles, because the evaporation rate difference of different elements can cause the deviation of composition, so, must carry out composition according to concrete alloy in the preparation and regulate.
Factors such as the ratio of adjusting hydrogen and argon gas, current value, atmosphere total pressure can be controlled at the size of particle nanometer or accurate nanoscale, and the composition of alloying pellet can be regulated by ratio, current value, the atmosphere total pressure factor of foundry alloy composition, hydrogen and argon gas.
Preparing ultra micro powder alloying pellet with hydrogen arc plasma process of the present invention, to have equipment simple, and aggregate velocity is fast, and cost is low, product purity height, advantage such as the ultra micro powder kind that can synthesize is many.The speed that forms nano particle under hydrogen arc plasma concrete conditions in the establishment of a specific crime is bigger several times to tens times than vacuum vapor deposition method, realizes suitability for industrialized production easily.Ultra micro powder material of the present invention is during as lithium ion battery negative material, and the specific capacity height is that the twice of graphite is many as the reversible specific capacity first of SnSb alloy; Prepared material is nanometer or accurate nano-scale, and particle is little, has better cyclical stability than micron order material; Prepared ultra micro powder microscopic appearance microspheroidal have than with the littler specific area of other pattern material of yardstick, thereby it is lower than the irreversible capacity first with the yardstick material.
Description of drawings
Fig. 1 is the used hydrogen arc-plasma preparation facilities schematic diagram of powder process of the present invention.
Fig. 2 is the transmission electron microscope photo of the prepared Sn-Sb alloy ultra micro powder of the present invention.
Fig. 3 is the cycle life curve chart of the prepared Sn-Sb alloy ultra micro powder of the present invention.
Fig. 4 is the transmission electron microscope photo of the prepared Si-Ni alloy ultra micro powder of the present invention.
Fig. 5 is current potential-specific volume spirogram that the prepared Si-Ni alloy ultra micro powder of the present invention circulates first.
Wherein:
1---electric arc reaction chamber 2---water-cooled copper base 3---tungsten electrode
4---DC power supply 5---particle collector 6---vacuum pumps
7---gas circulator
Embodiment
Embodiment 1: synthetic quasi-nano SnSb alloying pellet
(1) used hydrogen arc-plasma preparation facilities as shown in Figure 1, water-cooled copper plate is as anode, tungsten electrode is a negative electrode, in molar ratio the ratio of pure tin (purity＞99.9%) 70%, star antimony (purity＞99.9%) 30% is prepared burden, in argon gas atmosphere, obtain alloy pig with the arc heating melting, for composition is mixed, alloy pig will spin upside down 4 times;
(2) when carrying out the 4th melting, extract the part argon gas out, feed the hydrogen that accounts for cumulative volume 20%, metal evaporates in a large number and generates the ultra micro powder particles, and keeping the atmosphere total pressure in preparation process is 0.1Mpa, and electric current is 200A, voltage is 25V, and the circulating current of collecting granules is that 100L/min is constant;
(3) nano particle that obtains is carried out Passivation Treatment more than 24 hours with argon gas and Air mixing gas, prevent its spontaneous combustion in air.
(4) will collect with standby through the powder of Passivation Treatment.
Adopt the SnSb alloy nanoparticle of hydrogen arc plasma body method preparation not have impurity such as oxide basically, particle diameter is 1～300nm, as shown in Figure 2.The powder sample composition that obtains is for containing Sb 46.5at%, through electro-chemical test, the prepared SnSb alloy ultra micro powder of the present invention has very high specific capacity, embedding lithium capacity has reached 930mAh/g first, take off the lithium capacity first and reach 701mAh/g, and cyclical stability is better, and 20 times circulation back reversible specific capacity still reaches 566mAhg
-1, capability retention is that 81% (as shown in Figure 3, charging and discharging currents density is 50mA/g, and the charging/discharging voltage scope is 0～1.5V).
Embodiment 2: synthesis nano SiNi alloying pellet
(1) used hydrogen arc-plasma preparation facilities as shown in Figure 1, water-cooled copper plate is as anode, tungsten electrode is a negative electrode, the pure silicon ratio batching of pure silicon (purity＞99.9%) 80%, pure nickel (purity＞99.9%) 20% in molar ratio in molar ratio, in argon gas atmosphere, obtain alloy pig with the arc heating melting, for composition is mixed, alloy pig will spin upside down 4 times;
(2) when carrying out the 4th melting, extract the part argon gas out, feed the hydrogen that accounts for cumulative volume 50%, metal evaporates in a large number and generates the ultra micro powder particles, and keeping the atmosphere total pressure in preparation process is 0.1Mpa, and electric current is 200A, voltage is 25V, and the circulating current of collecting granules is that 100L/min is constant;
(3) nano particle that obtains is carried out Passivation Treatment more than 24 hours with argon gas and Air mixing gas, prevent its spontaneous combustion in air.
(4) will collect with standby through the powder of Passivation Treatment.
Prepared Si-Ni alloy nanoparticle is spherical in shape, and particle size is distributed between 20～50nm, mostly as shown in Figure 4.The powder sample composition is for containing Ni 9at%, through electro-chemical test, its first embedding lithium capacity reached 2208mAh/g, take off the lithium capacity first and reach 1304mAh/g (as shown in Figure 5, charging and discharging currents density is 50mA/g, and the charging/discharging voltage scope is 0～1.5V).
Claims (9)
1. the preparation method of a lithium ion battery alloy class negative material may further comprise the steps:
(1) smelt stage: each component that desire is prepared alloy is in predetermined ratio batching, be placed on the water-cooling subbase in the reaction cavity of a sealing, in inert atmosphere, obtain alloy pig with the arc heating melting, for each component is mixed, alloy pig will spin upside down and carry out repeatedly melting several times;
(2) the powder process stage: after smelt stage is finished, inert gas is taken out a part, feed a certain amount of hydrogen then, control arc current, arc voltage and atmosphere total pressure make alloy begin a large amount of evaporations and generation ultra micro powder particles;
(3) the passivation stage: after powder process is finished the ultra micro powder particles is carried out Passivation Treatment;
(4) collection phase: will collect with standby through the ultra micro powder particles of Passivation Treatment.
2. the method for claim 1 is characterized in that, described water-cooling subbase is a copper coin.
3. the method for claim 1 is characterized in that, in the described step (2) volume content of hydrogen greater than 0 smaller or equal to 100%.
4. method as claimed in claim 3 is characterized in that, the volume content of described hydrogen≤50%.
5. the method for claim 1 is characterized in that, the current value of described step (2) is 50～1000A, magnitude of voltage is＜and the safe voltage of 36V, the atmosphere total pressure is no more than 0.1Mpa.
6. method as claimed in claim 5 is characterized in that, described current value is 100～300A, and magnitude of voltage is 20～25V.
7. the method for claim 1 is characterized in that, the granularity of described ultra micro powder particles is 1～1000nm.
8. method as claimed in claim 7 is characterized in that, the granularity of described ultra micro powder particles is 1～300nm.
9. the method for claim 1 is characterized in that, described alloy ultra micro powder particles is SnSb, SnFe, SnNi, SiNi or SiFe alloy.
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| CNB200610012111XA CN100438149C (en) | 2006-06-06 | 2006-06-06 | Method for preparing high capacity lithium ion cells cathode material |
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| CNB200610012111XA CN100438149C (en) | 2006-06-06 | 2006-06-06 | Method for preparing high capacity lithium ion cells cathode material |
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| CN100438149C true CN100438149C (en) | 2008-11-26 |
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| CN105127414B (en) * | 2015-09-29 | 2017-05-31 | 安徽工业大学 | A kind of preparation method of core shell structure silver nickel coat nano-powder material |
| CN105720249B (en) * | 2016-02-22 | 2018-03-13 | 北京工业大学 | A kind of preparation method of Sn Si alloy-type nano composite powders |
| CN108063242B (en) * | 2017-12-11 | 2020-11-03 | 中国科学院过程工程研究所 | Silicon-based alloy material and preparation method and application thereof |
| CN108580916A (en) * | 2018-08-01 | 2018-09-28 | 重庆国际复合材料股份有限公司 | A kind of electric spark corrode prepares the reaction unit of metal powder |
| CN112551530A (en) * | 2020-11-26 | 2021-03-26 | 宁波广新纳米材料有限公司 | Production method of plasma transferred arc silicon powder |
| CN112496333A (en) * | 2020-11-26 | 2021-03-16 | 大连理工大学 | Preparation method and application of Si-Ti alloy nano powder |
| CN116014093A (en) * | 2022-12-15 | 2023-04-25 | 天津大学 | High-conductivity functional group heterogeneous-phase connection material at zinc grain boundary and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287694A (en) * | 1998-09-18 | 2001-03-14 | 佳能株式会社 | Electrode material for negative pole for lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure |
| WO2005031898A1 (en) * | 2003-09-26 | 2005-04-07 | Jfe Chemical Corporation | Composite particle and, utilizing the same, negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1287694A (en) * | 1998-09-18 | 2001-03-14 | 佳能株式会社 | Electrode material for negative pole for lithium secondary cell, electrode structure using said electrode material, lithium secondary cell using said electrode structure |
| WO2005031898A1 (en) * | 2003-09-26 | 2005-04-07 | Jfe Chemical Corporation | Composite particle and, utilizing the same, negative electrode material for lithium ion secondary battery, negative electrode and lithium ion secondary battery |
Non-Patent Citations (2)
| Title |
|---|
| 直流氢电弧等离子体蒸发法制备Cu-Ni纳米复合粉体. 高建卫，张振忠，张少明.铸造技术，第26卷第4期. 2005 |
| 直流氢电弧等离子体蒸发法制备Cu-Ni纳米复合粉体. 高建卫，张振忠，张少明.铸造技术，第26卷第4期. 2005 * |
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