CN105098164B - A kind of silicon lithium titanate cathode material and preparation method thereof - Google Patents
A kind of silicon lithium titanate cathode material and preparation method thereof Download PDFInfo
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- CN105098164B CN105098164B CN201410218384.4A CN201410218384A CN105098164B CN 105098164 B CN105098164 B CN 105098164B CN 201410218384 A CN201410218384 A CN 201410218384A CN 105098164 B CN105098164 B CN 105098164B
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Abstract
The present invention relates to a kind of negative material and preparation method thereof, especially suitable for a kind of silicon lithium titanate cathode material used in lithium ion battery and preparation method thereof.The raw material of the negative material includes lithium metal and silica flour.Silicon lithium material prepared by the present invention, as negative material when, can effectively improve the first charge-discharge efficiency of lithium ion battery.In addition, whole preparation process environmental pollution of the present invention is small, simple process and low cost, whole production process is easily controllable, meets the demand of large-scale production.
Description
Technical field
The present invention relates to a kind of negative material and preparation method thereof, especially suitable for a kind of silicon lithium used in lithium ion battery
Negative material and preparation method thereof.
Background technology
As people are higher and higher to the demand of new energy, lithium ion battery just has been more and more widely used.At present
Commercially use negative material is mostly graphite-like carbon negative pole material, but its theoretical lithium storage content is relatively low.Therefore, develop new
High-capacity cathode material becomes current research hotspot.Silicon due to very high theoretical lithium storage content (4200mAh/g), compared with
Low intercalation potential and cause extensive concern.But silica-base material, under conditions of height removal lithium embedded, there is serious body
Product effect, volume change is even up to 300%, so as to trigger cycle performance to decline.And in fact, as shown in Figure 7, full battery
Capacity rise with the rising of capacity of negative plates, and rise before capacity of negative plates reaches 500mAh/g most fast, hold in anode
Amount reaches basicly stable after 1000mAh/g.For a little lithiums of silica-base material preliminary filling, the portion capacity of silicon is only used, to the energy of full battery
Metric density does not influence, and can reduce the volumetric expansion of silicon.Also, silicon first charge-discharge efficiency is all than relatively low, with cathode
When match materials are into battery, substantial amounts of lithium ion is just consumed after charging in first time and can not return to cathode.It is original to use
The purpose of large capacity anode is exactly to increase the population size of battery, but first charge-discharge efficiency it is low can seriously reduce on the contrary lithium electricity
The actual capacity in pond, limits its application.The loss of irreversible capacity first directly results in the energy content of battery in lithium battery
Loss.Capacitance loss is actually the loss of lithium, for example efficiency is 75% first, then 25% lithium after charging in first time
Just irreversibly consume.Under normal circumstances, lithium is all from positive electrode, most expensive component in this lithium battery.To adopt
It is to solve the problems, such as this effectively method to provide other lithium source with the lithium battery of the negative material of large capacity.Application No.
201210193822.7 Chinese patent discloses a kind of siliceous cathode of lithium, its preparation method and the lithium sulphur electricity comprising the anode
Pond, the patent by electrochemical deposition method by lithium deposit to containing on silicium cathode to prepare silicon cathode of lithium.Although this method can be with
Obtain the silicon cathode of lithium containing lithium, but the patent is since using electrochemical deposition method, preparation process is complicated, of high cost,
And the silicon cathode of lithium stability made is poor；In addition, the patent is the performance improved as anode lithium in lithium-sulfur cell, and for silicon
Electrical property improves and does not study during as negative material.
The content of the invention
First purpose of the invention is to provide a kind of silicon lithium titanate cathode material, the raw material of the negative material include lithium metal and
Silica flour.
The high power capacity of silicon based anode material makes it very promising negative material.But it there are volumetric expansion and
The problem of efficiency is low first.Above-mentioned two problems can effectively be alleviated by mending lithium for silica-base material, therefore the present invention uses metal
Lithium for silica flour provide mend lithium needed for raw material, silicon lithium titanate cathode material is prepared, to solve above-mentioned two problems.Silicium cathode material is fitted
The benefit lithium of amount, can effectively make up lithium ion battery initial charge process consume lithium, electric discharge when can allow lithium from
Son is deviate from from silicium cathode material, improves first charge-discharge efficiency.The silicon based anode material that the present invention mends lithium can also be as negative
Pole additive, lithium is mended for full battery.
Further, the raw material of the negative material includes lithium metal and silica flour, and the lithium metal rubs with the silica flour
You are than being 0.1~4；Preferably, the molar ratio of the lithium metal and the silica flour is 0.5~3；As further preferred, institute
The molar ratio for stating lithium metal and the silica flour is 1~2.
The molar ratio of lithium metal and silica flour is 0.1~4 in the present invention, preferably, the molar ratio of lithium metal and silica flour is
0.5~3.As further preferred, the molar ratio of the lithium metal and the silica flour is 1~2.The proportioning may further ensure that
Contain enough lithiums in negative material prepared by the present invention, electricity when being used using the follow-up negative material of satisfaction as battery cathode
Performance.
Preferably, the lithium metal is bulk, sheet, powdery or filiform.
Lithium metal can exist in any form in the present invention：Such as bulk, sheet, powdery, filiform etc., can conduct
The present invention mends lithium material.Therefore, technique cost of manufacture is greatly reduced.
The silica flour is the one or more in millimeter powder, powder and micron and nano powder.
In the present invention, elemental lithium mass fraction can be greater than or equal to 95% in the lithium metal；Silicon member in the silica flour
The mass fraction of element can be greater than or equal to 90%.
Another object of the present invention is to provide the preparation method of the silicon lithium titanate cathode material, and lithium metal is mixed with silica flour
It is put into the reaction vessel full of inert gas and is reacted, after reaction through cooling down up to silicon cathode of lithium material of the present invention
Material.
The molar ratio of lithium metal and silica flour is 0.1~4 in the preparation method of silicon lithium titanate cathode material of the present invention, preferably,
The molar ratio of lithium metal and silica flour is 0.5~3.As further preferred, the molar ratio of the lithium metal and the silica flour for 1~
2.The proportioning, which may further ensure that in negative material prepared by the present invention, contains enough lithiums, to meet the follow-up negative material
Electrical property when being used as battery cathode.
Preferably, the temperature control of the reaction is 190~1320 DEG C.
Temperature range of the present invention can further make lithium metal be easier to fill into silicon, and the lithium for ensureing to fuse into is formed with silicon
Good combination, the method for the present invention can form Li-Si alloy, specific as reaction equation (1) represents：
Lithium metal is mixed with silica flour and is put into when being reacted in the reaction vessel full of inert gas, as further excellent
Choosing, the temperature control of the reaction is 250~900 DEG C.As further preferred, the temperature control of the reaction is 300~600
℃.As still more preferably, the temperature control of the reaction is 400~500 DEG C.
Preferably, when the time control of the reaction is small more than or equal to 0.5.Lithium metal is mixed to be put into silica flour and is filled
When being reacted in the reaction vessel of full inert gas, as further preferred, the time control of the reaction is small for 1~24
When.As further preferred, the time control of the reaction for 5~20 it is small when.As still more preferably, the reaction when
Between control for 10~15 it is small when.
Preferably, the inert gas is selected from least one of argon gas and helium.
Another object of the present invention is to provide a kind of anode prepared by silicon lithium titanate cathode material.
Last purpose of the invention is to provide a kind of lithium ion battery, contains silicon lithium titanate cathode material as described above.
Invention effect
The silicon lithium material of the present invention, as negative material when, can effectively improve the first charge-discharge effect of lithium ion battery
Rate.Lithium silicium cathode material manufacture craft of the present invention is simple, and cost is low, and operability is high, suitable for big industrial production demand；This
Outside, the present invention make in not only process parameter control it is few and it is of the invention needed for control technological parameter be also easy to automatically control, because
This ensure that the uniformity and stability of lithium silicium cathode quality of materials prepared by the present invention, meet industrial production demand.
Brief description of the drawings
Fig. 1：The SEM figures of silicon lithium material prepared by the embodiment of the present invention 1；
Fig. 2：The XRD diagram of silicon lithium material prepared by the embodiment of the present invention 1；
Fig. 3：The SEM figures of silicon lithium material prepared by the embodiment of the present invention 2；
Fig. 4：The XRD diagram of silicon lithium material prepared by the embodiment of the present invention 2；
Fig. 5：The SEM figures of silicon lithium material prepared by the embodiment of the present invention 3；
Fig. 6：The XRD diagram of silicon lithium material prepared by the embodiment of the present invention 3；
Fig. 7：The graph of a relation of negative material specific capacity and full battery specific capacity；
Fig. 8：Silicon lithium material prepared by the embodiment of the present invention 3 makees the electrical property curve map of negative plate.
Embodiment
The present invention is described in detail in following specific embodiment, but the present invention is not restricted to following implementation
Example.
Embodiment 1：
According to lithium and the molar ratio n=0.5 of micron silica flour, 0.15g lithium pieces and 1.2g micron silicons are placed in reaction kettle；Will
Reaction kettle is placed in tube furnace, and under argon gas protection, reaction kettle is risen to 700 DEG C of insulations by room temperature with 5 DEG C/min heating rates
2h, obtains silicon lithium material after natural cooling.Fig. 1 (a) and Fig. 1 (b) is the silicon lithium material that the embodiment of the present invention 1 is prepared respectively
The SEM figures of material, wherein Fig. 1 (a) amplification factors are 2000 times；Wherein Fig. 1 (b) amplification factors are 10000 times.Fig. 2 is the present invention
The XRD diagram for the silicon lithium material that embodiment 1 is prepared.
Embodiment 2：
According to lithium and the molar ratio n=1 of micron silica flour, 0.3g lithium pieces and 1.2g micron silicons are placed in reaction kettle；Will be anti-
Answer kettle to be placed in tube furnace, under argon gas protection, reaction kettle risen to by 700 DEG C of insulation 2h by room temperature with 5 DEG C/min heating rates,
Silicon lithium material is obtained after natural cooling.Fig. 3 (c) and Fig. 3 (d) is the silicon lithium material that the embodiment of the present invention 2 is prepared respectively
SEM figure, wherein Fig. 3 (c) amplification factors be 2000 times；Wherein Fig. 3 (d) amplification factors are 5000 times.Fig. 4 is implementation of the present invention
The XRD diagram for the silicon lithium material that example 2 is prepared.
Embodiment 3：
According to lithium and the molar ratio n=3 of micron silica flour, 0.9g lithium pieces and 1.2g micron silicons are placed in reaction kettle；Will be anti-
Answer kettle to be placed in homogeneous reactor, under argon gas protection, reaction kettle is risen to by 250 DEG C of guarantors by room temperature with 5 DEG C/min heating rates
Warm 24h, obtains silicon lithium material after natural cooling.Fig. 5 (e) and Fig. 5 (f) is the silicon that the embodiment of the present invention 3 is prepared respectively
The SEM figures of lithium material, wherein Fig. 5 (e) amplification factors are 2000 times；Wherein Fig. 5 (f) amplification factors are 5000 times.Fig. 6 is this hair
The XRD diagram for the silicon lithium material that bright embodiment 3 is prepared.
Silicon lithium material prepared by the embodiment of the present invention 3 is made into negative plate, with nickle cobalt lithium manganate (NCM) for positive electrode, is adopted
Battery is assembled into lithium hexafluoro phosphate carbonic ester electrolyte and PVDF membranes, to the test knot of its specific discharge capacity and coulombic efficiency
Fruit is as shown in Figure 8.
This electric performance test condition is：Charging process keeps constant-voltage charge, charge cutoff electric current with blanking voltage 4.3V
For 0.01mA, blanking voltage is 2.5V in discharge process.In addition, in order to test the electrical property under different charge-discharge magnifications, this
First time, cycle charge-discharge multiplying power was 0.1C in test；Second of cycle charge-discharge multiplying power is 0.2C；When third time circulates
Rate of charge is 0.2C, discharge-rate 1.0C；Rate of charge is 0.2C, discharge-rate 5.0C during the 4th circulation；5th
Rate of charge is 1.0C, discharge-rate 1.0C during secondary circulation；It is identical with the 5th time from the test condition after the 5th time.
Embodiment 4：
According to lithium and the molar ratio n=0.1 of silica flour, the silica flour is micron silica flour and nano silica fume, by lithium block and silica flour
It is placed in reaction kettle；Reaction kettle is placed in homogeneous reactor, under argon gas protection, with 5 DEG C/min heating rates by reaction kettle
400 DEG C of insulation 15h are risen to by room temperature, silicon lithium material is obtained after natural cooling.
Embodiment 5：
According to lithium and the molar ratio n=2 of silica flour, the silica flour is micron silica flour, nano silica fume and millimeter silica flour, by lithium
Powder and silica flour are placed in reaction kettle；Reaction kettle is placed in homogeneous reactor, under argon gas protection, with 5 DEG C/min heating rates
Reaction kettle is risen into 900 DEG C of insulation 8h by room temperature, silicon lithium material is obtained after natural cooling.
Embodiment 6：
According to lithium and the molar ratio n=4 of nano silica fume, lithium silk and silica flour are placed in reaction kettle；Reaction kettle is placed in
In phase reaction device, under argon gas protection, reaction kettle is risen to by 1300 DEG C of insulation 0.5h by room temperature with 5 DEG C/min heating rates, from
So silicon lithium material is obtained after cooling.
Conclusion：The Li0.5Si that detects of attached drawing 2 in being tested with reference to XRD of the present invention, LiSi that attached drawing 4 detects and attached
Granule-morphology can in tri- kinds of materials of Li3Si that Fig. 6 is detected, and the corresponding SEM figures of three kinds of materials on detecting
Know：Swell with the gradual of volume of silica flour, silicon powder particle volume is increasing as shown in Fig. 1 to Fig. 3 to Fig. 5；Silicon lithium alloy
Ratio it is increasing, the ratio of silicon lithium alloy is increasing as shown in attached drawing 2 to Fig. 4 to Fig. 6.Illustrate that the technology of the present invention can be with
Lithium effectively is mended to silicon, and prepares that component is pure, constitutionally stable Li-Si alloy.
Claims (7)
- A kind of 1. preparation method of silicon lithium titanate cathode material, it is characterised in that：The raw material of the negative material includes lithium metal and silicon Powder；Lithium metal is mixed to be put into the reaction vessel full of inert gas with silica flour and is reacted, is through cooling after reaction Obtain silicon lithium titanate cathode material；The molar ratio of the lithium metal and the silica flour is 0.5~3；The temperature control of the reaction for 300~ 600℃；When the time control of the reaction is 5~20 small.
- 2. the preparation method of silicon lithium titanate cathode material as claimed in claim 1, it is characterised in that：The lithium metal is block, piece Shape, powdery or filiform.
- 3. the preparation method of silicon lithium titanate cathode material as claimed in claim 1, it is characterised in that：The silica flour is millimeter powder, micro- One or more in rice flour and nano powder.
- 4. the preparation method of silicon lithium titanate cathode material as claimed in claim 1, it is characterised in that：The inert gas is selected from argon gas At least one of with helium.
- 5. silicon lithium titanate cathode material prepared by a kind of preparation method of silicon lithium titanate cathode material as described in claim 1.
- A kind of 6. anode prepared by silicon lithium titanate cathode material as described in claim 5.
- 7. a kind of lithium ion battery, contains silicon lithium titanate cathode material as claimed in claim 5.
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| CN107093708A (en) * | 2017-03-27 | 2017-08-25 | 南昌大学 | A kind of preparation method of full n-type silicon lithium ion battery negative material |
| CN111916704B (en) * | 2020-08-04 | 2023-02-21 | 珠海冠宇电池股份有限公司 | Negative electrode material, preparation method, negative plate and battery |
| CN112531161B (en) * | 2020-11-30 | 2022-04-29 | 蜂巢能源科技有限公司 | Pre-lithium negative electrode material, preparation method thereof, pre-lithium negative electrode and pre-lithium battery |
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| CN101510602B (en) * | 2009-02-19 | 2010-11-03 | 上海交通大学 | Method for preparing silicon composite cathode material of lithium ion battery |
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