CN101465418B - Method for preparing composite material for lithium ion secondary battery anode - Google Patents
Method for preparing composite material for lithium ion secondary battery anode Download PDFInfo
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- CN101465418B CN101465418B CN200710300671XA CN200710300671A CN101465418B CN 101465418 B CN101465418 B CN 101465418B CN 200710300671X A CN200710300671X A CN 200710300671XA CN 200710300671 A CN200710300671 A CN 200710300671A CN 101465418 B CN101465418 B CN 101465418B
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Abstract
The invention provides a preparation method of anode composite material for lithium-ion secondary battery; impacting flow is formed by rotary jetting along the upward direction by a first medium flow and a second medium flow, and the rotary directions of the first medium flow and the second medium flow are opposite, under the state, precursor particles of the clad material and anode active material particles which are with opposite rotary directions carry out high-speed rotary collision, thus leading the precursor particles of the clad material to be uniformly coated on the surfaces of the anode active material particles; in addition, the coated anode active material particles flow circularly under the gravity action and the blast air action below the particles and carry out collision again with the precursor particles of the clad material jetted below the anode active material particles, thus further strengthening the coating effect and leading the anode active material to be separated from the electrolyte, effectively preventing the mutual action of the precursor particles of the clad material and the anode active material particles and improving safety performance of the obtained battery when in high temperature and over-charging condition.
Description
Technical field
The invention relates to a kind of preparation method of composite material for lithium ion secondary battery anode.
Background technology
Lithium ion battery has operating voltage height, in light weight, outstanding feature such as energy density is big, self discharge is little, have extended cycle life, memory-less effect, non-environmental-pollution, security performance are good, it is the higher a kind of portable ideal battery of present capacitance, can be applicable to electronic installations such as video camera, mobile phone, notebook computer and Portable Measurement Instrument, also is the first-selected power supply of light-duty high-energy power batteries such as following electric automobile, space flight, satellite, submarine, underwater robot.
Lithium ion battery is widely used owing to having premium properties, and along with developing rapidly of products such as modern mobile electronic device and communication apparatus, people are to being used for the demands for higher performance of these product power supplys.
Cell positive material is one of key technology of lithium ion battery development.In the positive active material of commercial at present lithium rechargeable battery, mainly comprise lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium nickel cobalt manganese oxygen, LiFePO4 etc., since positive active material over-charging of battery or when overheated can with electrolyte generation vigorous reaction, therefore, by being a kind of simple and effective method of modifying positive active material being carried out the surface coats.This method is by coating the thin and stable barrier of one deck on the positive active material surface, positive active material and electrolyte are kept apart, can effectively stop the interaction between the two, thereby improve the battery obtain at high temperature with the security performance when overcharging.
For example, CN1879957A discloses a kind of overcritical percussion flow particle method for coating, and this method comprises: (1) will coat the wall material of usefulness and be added in the dissolving blender CO by coated particle
2Add in the dissolving blender by the high-pressure diaphragm pump back of boosting, heat up for the dissolving blender, make to coat the wall material and be dissolved in supercritical CO by constant temperature bath
2In form solution, and make to be dispersed in this solution by stirring and form suspension by coated pellet; (2) this suspension forms percussion flow by a pair of coaxial nozzle ejection in opposite directions to coating in the device; (3) be dissolved in supercritical CO
2In coating wall material separate out from this solution by nozzle expansion decompression back, and be deposited on by the coated pellet surface and form even cortex; (4) microcapsules and the CO that in the dissolving blender, after coating, forms
2Gas enters separator to be separated, and the solid phase microcapsules are received and kept as product.But the shortcoming that this method exists is that covered effect is relatively poor, can't be in the uniform wrapped by separator of positive active material particle surface, thereby positive active material and electrolyte are kept apart, and the battery that obtains is still relatively poor at high temperature and the security performance when overcharging.
Summary of the invention
The objective of the invention is for the covered effect that overcomes the positive electrode that prior preparation method obtains poor, cause the lithium ion battery that obtains at high temperature with the shortcoming of the poor safety performance when overcharging, provide a kind of covered effect good, can make the lithium ion battery that obtains have at high temperature with when overcharging excellent safety can the preparation method of composite material for lithium ion secondary battery anode.
The inventor has carried out careful research to prior preparation method, finds that existing method is by being dispersed in supercritical CO with clad material presoma and encapsulated material
2The middle suspension that forms in device forms percussion flow by a pair of coaxial nozzle ejection in opposite directions to coating with this suspension afterwards, is dissolved in supercritical CO
2In the clad material presoma separate out from this solution by nozzle expansion decompression back, and be deposited on the encapsulated material, but because the restriction of bump mode between clad material presoma and the encapsulated material, can't form uniform coating layer on the encapsulated material surface, cause adopting this method poor, thereby influenced the lithium ion battery that obtains at high temperature with the security performance when overcharging at the covered effect of positive electrode surface wrapped by separator.
The invention provides a kind of preparation method of composite material for lithium ion secondary battery anode, wherein, this method comprises the clad material presoma is dissolved in supercritical CO
2Middle first MEDIA FLOW that forms; Positive active material is suspended in formation second MEDIA FLOW in the protective gas; Simultaneously first MEDIA FLOW and second MEDIA FLOW are rotated injection formation percussion flow, the positive active material particle that obtains having the clad material precursor layer with the injection direction that makes progress afterwards; The positive active material particle with clad material precursor layer that will obtain afterwards carries out sintering, obtains anode composite material; Wherein, when rotary-jet, first MEDIA FLOW be looped around second MEDIA FLOW around, and the direction of rotation of first MEDIA FLOW is opposite with the direction of rotation of second MEDIA FLOW.
The present invention is by being rotated injection formation percussion flow with first MEDIA FLOW and second MEDIA FLOW with the injection direction that makes progress, and the direction of rotation of first MEDIA FLOW is opposite with the direction of rotation of second MEDIA FLOW, in this state, clad material granular precursor that direction of rotation is opposite and positive active material particle carry out the high speed rotating collision, can make the clad material granular precursor be coated on the surface of positive active material particle uniformly, and, positive active material particle after the coating is subjected to the effect of gravity and the air blast effect of below circulates, bump with below ejection clad material granular precursor once more, further strengthened the effect that coats, thereby positive active material and electrolyte are kept apart, effectively stop the interaction between the two, improve the battery that obtains at high temperature with the security performance when overcharging.
Description of drawings
Fig. 1 is the structural representation of device therefor among the embodiment of the invention 1-4.
Description of reference numerals:
1-first inlet
2-second inlet
The bassoon of 3-nozzle
4-nozzle tubule
5-first swirler
6-second swirler
The 7-Laval pipe
The 8-narrow annular channel
The 9-expansion chamber
Embodiment
The preparation method of composite material for lithium ion secondary battery anode provided by the invention comprises the clad material presoma is dissolved in supercritical CO
2Middle first MEDIA FLOW that forms; Positive active material is suspended in formation second MEDIA FLOW in the protective gas; Simultaneously first MEDIA FLOW and second MEDIA FLOW are rotated injection formation percussion flow, the positive active material particle that obtains having the clad material precursor layer with the injection direction that makes progress afterwards; The positive active material particle with clad material precursor layer that will obtain afterwards carries out sintering, obtains anode composite material; Wherein, when rotary-jet, first MEDIA FLOW be looped around second MEDIA FLOW around, and the direction of rotation of first MEDIA FLOW is opposite with the direction of rotation of second MEDIA FLOW.
Described supercritical CO
2Be meant the CO that is in supercriticality
2, wherein liquid and gas become poised state point critical point, the temperature and pressure when critical point is called critical pressure; Be higher than critical temperature and critical pressure and be called supercriticality near the state of critical point.
Among the present invention, the rotary speed and the jet velocity of described first MEDIA FLOW and second MEDIA FLOW can in very large range change, but in order to make the positive active material particle surface form the clad material precursor layer of even compact, under the preferable case, the Mach 2 ship 0.2-0.8 of the jet velocity of described first MEDIA FLOW, the rotary speed of described first MEDIA FLOW is 2000-10000 rev/min; The Mach 2 ship 1-1.8 of the jet velocity of described second MEDIA FLOW, the rotary speed of described second MEDIA FLOW is 2000-10000; More preferably, the Mach 2 ship 0.5-0.8 of the jet velocity of described first MEDIA FLOW, the rotary speed of described first MEDIA FLOW is 4000-8000 rev/min; The Mach 2 ship 1-1.5 of the jet velocity of described second MEDIA FLOW, the rotary speed of described second MEDIA FLOW is 4000-8000 rev/min, described Mach number is meant the ratio of fluid velocity and local velocity of sound.
The described injection direction that makes progress can change in very big angular range; Under the preferable case, injection direction can be horizontal by the 45-90 degree; More preferably, horizontal by 90 angles of spending.
According to the present invention, the consumption of described positive active material and clad material presoma can in very large range change, and under the preferable case, with respect to the positive active material of 100 weight portions, the consumption of described clad material presoma is the 0.1-25 weight portion; More preferably, with respect to the positive active material of 100 weight portions, the consumption of described clad material presoma is the 0.5-15 weight portion.
According to the present invention, when rotary-jet, described first MEDIA FLOW be looped around second MEDIA FLOW around be meant first MEDIA FLOW the ejection moment be looped around second MEDIA FLOW around, clad material granular precursor in first MEDIA FLOW of ejection back carries out the high speed rotating collision with the positive active material particle with opposite direction of rotation, thereby make the clad material granular precursor be coated on the surface of positive active material particle uniformly, and, positive active material particle after the coating is subjected to the effect of gravity and the air blast effect of below circulates, bump with below ejection clad material granular precursor once more, further strengthened the effect that coats.
Among the present invention, described positive active material can be the positive active material of the various routines that are used for lithium ion battery, and for example, described positive active material can be in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium nickel cobalt manganese oxygen and the LiFePO4 one or more; The size of described positive active material particle can in very large range change, under the preferable case, the mean particle diameter of described positive active material particle is the 1-200 micron, the positive active material that meets above-mentioned condition can be commercially available, for example, lithium cobalt oxygen, lithium manganese oxygen and the lithium nickel cobalt manganese oxygen etc. of the production of Hunan China fir China fir company.
Described clad material presoma can be the various presomas that are used for the clad material of coated lithium ion battery positive active material.Described clad material can be non-noble metal oxide and/or silicon dioxide, and the example of non-noble metal oxide includes but not limited to aluminium oxide, magnesium oxide, zinc oxide, titanium oxide, cobalt oxide and zirconia.Described clad material presoma can be selected from corresponding salt of above-mentioned clad material and hydroxide thereof in one or more, be that aluminium oxide is an example with the clad material, the presoma of aluminium oxide can be aluminum nitrate and/or aluminium hydroxide; With the clad material is that silicon dioxide is example, and the presoma of silicon dioxide can be in silicon gel, Ludox and the waterglass one or more.
Among the present invention, the described preparation method who is used for the anode composite material of lithium ion battery can realize by various device, for example, can use equipment shown in Figure 1 to carry out the coating of clad material presoma at the positive active material particle surface, wherein, the clad material presoma is dissolved in supercritical CO
2In and the state that reaches capacity form later on first MEDIA FLOW, first MEDIA FLOW enters the nozzle bassoon 3 from first inlet 1; The positive active material particle suspending is formed second MEDIA FLOW in protective gas, second MEDIA FLOW enters the nozzle tubule 4 from second inlet 2; Second MEDIA FLOW can be sprayed with ultrasonic speed under the effect of pressure and Laval pipe 7; Under the effect of second swirler 6, second MEDIA FLOW also is rotated in high velocity jet simultaneously; Under the effect of the pressure and first swirler 5, first MEDIA FLOW also is rotated in high velocity jet, the direction of rotation of first MEDIA FLOW is opposite with second MEDIA FLOW, when rotary-jet, from narrow annular channel 8 ejections, described second MEDIA FLOW sprays from Laval pipe 7 by nozzle tubule 4 described first MEDIA FLOW by nozzle bassoon 3; And in the moment of ejection, first MEDIA FLOW be looped around second MEDIA FLOW around, in this case, clad material granular precursor that direction of rotation is opposite and positive active material particle carry out the high speed rotating collision, can make the clad material granular precursor be coated on the surface of positive active material particle uniformly; And the positive active material particle after the coating is subjected to the effect of gravity and the air blast effect of below circulates, and bumps with below ejection clad material granular precursor once more, has further strengthened the effect that coats.The middle part caliber of described Laval pipe 7 is less than the caliber at two ends, can make the jet velocity of second MEDIA FLOW reach supersonic speed, thereby make the collision of clad material granular precursor and positive active material particle more violent, make the better effects if of coating, described Laval pipe can be commercially available, for example, Qian Zhou credit in Wuxi reaches the laval pipe that machinery plant produces.
According to the present invention, described sintering with appointed condition be conventionally known to one of skill in the art, the little Muffle furnace that for example can use Jiangsu Wan Shi company to produce carries out sintering, and the condition of described sintering comprises that sintering temperature is 400-600 ℃, and sintering time is 200-400 minute.
To further specify the present invention by embodiment below.
Embodiment 1
Present embodiment is used to illustrate the preparation method who is used for the anode composite material of lithium ion battery provided by the invention.
(1) aluminum nitrates with 430 grams place extraction kettle, simultaneously by the high-pressure diaphragm pump pipeline that boosts, with CO
2In temperature is that 31.1 ℃, pressure are to heat under the condition of 7.3MPa to obtain supercritical CO
2, afterwards with supercritical CO
2In addition the speed of 50ml/min is sent in the high pressure extraction still, and the pressure in the extraction kettle is 20MPa, and temperature is 45 ℃, extracts that aluminum nitrate is dissolved in supercritical CO fully after 60 minutes
2In and the state that reaches capacity, obtain first MEDIA FLOW.
(2) in the powder conveying pump, 2000 gram lithium nickel cobalt manganese oxygens (Hunan China fir China fir, mean particle diameter are 150 microns) are suspended in the argon gas, obtain second MEDIA FLOW.
(3) first MEDIA FLOW enter the nozzle bassoon 3 from first inlet 1, and second MEDIA FLOW enters the nozzle tubule 4 from second inlet 2; Become the direction of 90 degree upwards to spray with second MEDIA FLOW with the same level face first MEDIA FLOW simultaneously afterwards, wherein, first MEDIA FLOW is from narrow annular channel 8 ejections, regulate the Mach 2 ship 0.7 of the jet velocity of first MEDIA FLOW by the speed control table, and the rotary speed of regulating first MEDIA FLOW by first swirler 5 is 10000 rev/mins; Second MEDIA FLOW regulate the Mach 2 ship 1.8 of the jet velocity of second MEDIA FLOW by spraying fast controller, and the rotary speed of regulating second MEDIA FLOW by second swirler 6 is 2000 rev/mins from Laval pipe 7 (Qian Zhou credit in Wuxi reaches machinery plant) ejection; Injecting time is 20 minutes, obtains the lithium nickel cobalt manganese oxygen that 2420 grams have the aluminum nitrate coating layer.
(4) lithium nickel cobalt manganese oxygen that 2420 grams that step (3) obtained have an aluminum nitrate coating layer is placed in the little Muffle furnace (Jiangsu Wan Shi company) and carries out sintering, and the temperature of sintering is 600 ℃, and the time of sintering is 200 minutes, obtains 2200g anode composite material A1.
Comparative Examples 1
Prepare reference anode composite material CA1 according to the method identical with embodiment 1, difference is, the Mach 2 ship 0.7 of the jet velocity of described second MEDIA FLOW, and first MEDIA FLOW and second MEDIA FLOW rotary speed be 0.
Embodiment 2
Present embodiment is used to illustrate the preparation method who is used for the anode composite material of lithium ion battery provided by the invention.
(1) magnesium nitrates with 120 grams place extraction kettle, simultaneously by the high-pressure diaphragm pump pipeline that boosts, with CO
2In temperature is that 31.1 ℃, pressure are to heat under the condition of 7.3MPa to obtain supercritical CO
2, afterwards with supercritical CO
2In addition the speed of 50ml/min is sent in the high pressure extraction still, and the pressure in the extraction kettle is 20MPa, and temperature is 45 ℃, extracts that magnesium nitrate is dissolved in supercritical CO fully after 40 minutes
2In and the state that reaches capacity, obtain first MEDIA FLOW.
(2) in the powder conveying pump, 2000 gram LiFePO4s (Hunan China fir China fir, mean particle diameter are 5 microns) are suspended in the argon gas, obtain second MEDIA FLOW.
(3) first MEDIA FLOW enter the nozzle bassoon 3 from first inlet 1, and second MEDIA FLOW enters the nozzle tubule 4 from second inlet 2; Become the direction of 90 degree upwards to spray with second MEDIA FLOW with the same level face first MEDIA FLOW simultaneously afterwards, wherein, first MEDIA FLOW is from narrow annular channel 8 ejections, regulate the Mach 2 ship 0.8 of the jet velocity of first MEDIA FLOW by the speed control table, and the rotary speed of regulating first MEDIA FLOW by first swirler 5 is 2000 rev/mins; Second MEDIA FLOW regulate the Mach 2 ship 1.1 of the jet velocity of second MEDIA FLOW by spraying fast controller, and the rotary speed of regulating second MEDIA FLOW by second swirler 6 is 10000 rev/mins from Laval pipe 7 (Qian Zhou credit in Wuxi reaches machinery plant) ejection; Injecting time is 10 minutes, obtains the LiFePO4 that 2111 grams have the magnesium nitrate coating layer.
(4) LiFePO4 that 2111 grams that step (3) obtained have a magnesium nitrate coating layer is placed in the little Muffle furnace (Jiangsu Wan Shi company) and carries out sintering, and the temperature of sintering is 400 ℃, and the time of sintering is 400 minutes, obtains 2030g anode composite material A2.
Embodiment 3
Present embodiment is used to illustrate the preparation method who is used for the anode composite material of lithium ion battery provided by the invention.
(1) aluminium hydroxides with 20 grams place extraction kettle, simultaneously by the high-pressure diaphragm pump pipeline that boosts, with CO
2In temperature is that 31.1 ℃, pressure are to heat under the condition of 7.3MPa to obtain supercritical CO
2, afterwards with supercritical CO
2Send in the extraction kettle with the speed of 50ml/min, the pressure in the extraction kettle is 20MPa, and temperature is 45 ℃, extracts that aluminium hydroxide is dissolved in supercritical CO fully after 20 minutes
2In and the state that reaches capacity, obtain first MEDIA FLOW.
(2) in the powder conveying pump, 2000 gram lithium cobalt oxygen (Hunan China fir China fir, mean particle diameter are 10 microns) are suspended in the argon gas, obtain second MEDIA FLOW.
(3) first MEDIA FLOW enter the nozzle bassoon 3 from first inlet 1, and second MEDIA FLOW enters the nozzle tubule 4 from second inlet 2; Become the direction of 90 degree upwards to spray with second MEDIA FLOW with the same level face first MEDIA FLOW simultaneously afterwards, wherein, first MEDIA FLOW is from narrow annular channel 8 ejections, regulate the Mach 2 ship 0.5 of the jet velocity of first MEDIA FLOW by the speed control table, and the rotary speed of regulating first MEDIA FLOW by first swirler 5 is 8000 rev/mins; Second MEDIA FLOW regulate the Mach 2 ship 1.5 of the jet velocity of second MEDIA FLOW by spraying fast controller, and the rotary speed of regulating second MEDIA FLOW by second swirler 6 is 4000 rev/mins from Laval pipe 7 (Qian Zhou credit in Wuxi reaches machinery plant) ejection; Injecting time is 2 minutes, obtains the lithium cobalt oxygen that 2016 grams have the aluminium hydroxide coating layer.
(4) the lithium cobalt oxygen that 2016 grams that step (3) obtained have an aluminium hydroxide coating layer is placed in the little Muffle furnace (Jiangsu Wan Shi company) and carries out sintering, and the temperature of sintering is 550 ℃, and the time of sintering is 300 minutes, obtains 2010g anode composite material A3.
Embodiment 4
Present embodiment is used to illustrate the preparation method who is used for the anode composite material of lithium ion battery provided by the invention.
(1) zinc nitrates with 200 grams place extraction kettle, simultaneously by the high-pressure diaphragm pump pipeline that boosts, with CO
2In temperature is that 31.1 ℃, pressure are to heat under the condition of 7.3MPa to obtain supercritical CO
2, afterwards with supercritical CO
2Send in the extraction kettle with the speed of 50ml/min, the pressure in the extraction kettle is 20MPa, and temperature is 45 ℃, extracts that zinc nitrate is dissolved in supercritical CO fully after 30 minutes
2In and the state that reaches capacity, obtain first MEDIA FLOW.
(2) in the powder conveying pump, 2000 gram lithium nickel cobalt manganese oxygens (Hunan China fir China fir, mean particle diameter are 30 microns) are suspended in the argon gas, obtain second MEDIA FLOW.
(3) first MEDIA FLOW enter the nozzle bassoon 3 from first inlet 1, and second MEDIA FLOW enters the nozzle tubule 4 from second inlet 2; Become the direction of 90 degree upwards to spray with second MEDIA FLOW with the same level face first MEDIA FLOW simultaneously afterwards, wherein, first MEDIA FLOW is from narrow annular channel 8 ejections, regulate the jet velocity Mach 2 ship 0.6 of first MEDIA FLOW by the speed control table, and the rotary speed of regulating first MEDIA FLOW by first swirler 5 is 5000 rev/mins; Second MEDIA FLOW regulate the Mach 2 ship 1.2 of the jet velocity of second MEDIA FLOW by spraying fast controller, and the rotary speed of regulating second MEDIA FLOW by second swirler 6 is 5000 rev/mins from Laval pipe 7 (Qian Zhou credit in Wuxi reaches machinery plant) ejection; Injecting time is 5 minutes, obtains the lithium nickel cobalt manganese oxygen that 2150 grams have the zinc nitrate coating layer.
(4) lithium nickel cobalt manganese oxygen that 2150 grams that step (3) obtained have a zinc nitrate coating layer is placed in the little Muffle furnace (Jiangsu Wan Shi company) and carries out sintering, and the temperature of sintering is 600 ℃, and the time of sintering is 360 minutes, obtains 2064 gram anode composite material A4.
Embodiment 5
(1) anode composite material A1 that 100 gram embodiment 1 are obtained and 4.5 gram Kynoar join in the 80 gram N-N-methyl-2-2-pyrrolidone N-s, stir in de-airing mixer then and form uniform anode sizing agent.This slurry is coated on the aluminium foil equably, following dry 15 hours at 50 ℃ then; Roll afterwards, the condition of described calendering comprises that the pressure of calendering is 1.5 MPas, and the time of calendering is 4 seconds; Cut to make and be of a size of 540 * 43.5 millimeters anodal B5, wherein contain 7.6 gram anode composite material A1.
(2) be that mixture, the 4 gram conductive agent carbon blacks that 1 gram carboxymethyl cellulose and 3 restrains butadiene-styrene rubber join in the 120 gram water with 100 gram negative electrode active composition native graphites, adhesive, in de-airing mixer, stir then and form uniform cathode size.This slurry is coated on the Copper Foil equably, following dry 15 hours at 50 ℃ then; Roll afterwards, the condition of described calendering comprises that the pressure of calendering is 1.5 MPas, and the time of calendering is 4 seconds; Cut to make and be of a size of 500 * 44 millimeters negative pole, wherein contain 2.6 gram active component native graphites.
(3) above-mentioned positive and negative electrode and polypropylene screen are wound into the pole piece of a square lithium ion battery, subsequently with LiPF
6Concentration by 1 mol is dissolved in EC/DMC=1: form nonaqueous electrolytic solution in 1 the mixed solvent, this electrolyte is injected battery case with the amount of 3.8g/Ah, lithium ion battery Z1 is made in sealing.
Comparative Examples 2
According to the method identical with embodiment 2, preparation reference lithium ion battery CZ1, the anode composite material A1 that the reference anode composite material CA1 alternate embodiment 1 that difference is to use Comparative Examples 1 to obtain obtains.
Embodiment 6-8
According to the method identical with embodiment 2, preparation lithium ion battery Z2-Z4, the anode composite material A1 that the anode composite material A2-A4 alternate embodiment 1 that difference is to use embodiment 2-4 to obtain respectively obtains.
Embodiment 9-12
The lithium ion battery Z1-Z4 that embodiment 5-8 is made carries out the acupuncture temperature detection and the maximum temperature detection of overcharging in accordance with the following methods, and test result is as shown in table 1.
The acupuncture temperature detection:
With battery with the 1C current charges to 4.2V, stop electric current 100mA, in safety cage, pierce through battery with the speed of 5mm/s then with the iron nail of φ=2.5mm, temperature with the battery surface of TES1310 digital display thermometer record after one minute, when the temperature of battery surface is reduced to below 40 ℃, battery is blasted or on fire after finish experiment, thereby obtain the maximum temperature of battery surface.
The maximum temperature of overcharging detects:
Battery is put into safety box, and battery plus-negative plate is connected with constant current constant voltage source, data collecting instrument; Thermometer probe is attached on the battery with the high temperature adhesive plaster, the induced cell temperature; Agilent constant current constant voltage source voltage is transferred to 12V, and electric current transfers to 0.95A; The variation of switch power supply and detail record battery voltage, temperature, electric current in test process.
Comparative Examples 3
According to the described method of embodiment 9-12, Comparative Examples 2 is made reference lithium ion battery CZ1, carry out the acupuncture temperature test and the maximum temperature detection of overcharging, the result is as shown in table 1
Table 1
| The embodiment numbering | The battery numbering | The acupuncture temperature (℃) | Overcharge maximum temperature (℃) |
| Embodiment 9 | Z1 | 100 | 60 |
| Embodiment 10 | Z2 | 95 | 50 |
| Embodiment 11 | Z3 | 100 | 55 |
| Embodiment 12 | Z4 | 110 | 65 |
| Comparative Examples 3 | CZ1 | (480.4 battery catches fire) | (576.2 battery explosion) |
From the result of last table 1 as can be seen, the acupuncture temperature of the battery Z1-Z4 that the anode composite material A1-A4 that uses embodiment of the invention 1-4 to make makes and the maximum temperature of overcharging all are starkly lower than the acupuncture temperature and the maximum temperature of overcharging of the reference cell CZ1 that the reference anode composite material CA1 that uses Comparative Examples 1 to make makes, coating layer that the preparation method who is used for the anode composite material of lithium ion cell positive provided by the invention can make positive active material particle surface even compact more is described, thereby positive active material and electrolyte are kept apart, effectively stop the interaction between the two, improve the battery that obtains at high temperature with the security performance when overcharging.
Claims (8)
1. the preparation method of a composite material for lithium ion secondary battery anode is characterized in that, this method comprises the clad material presoma is dissolved in supercritical CO
2Middle first MEDIA FLOW that forms; The positive active material particle suspending is formed second MEDIA FLOW in protective gas; Simultaneously first MEDIA FLOW and second MEDIA FLOW are rotated injection formation percussion flow, the positive active material particle that obtains having the clad material precursor layer with the injection direction that makes progress afterwards; The positive active material particle with clad material precursor layer that will obtain afterwards carries out sintering, obtains anode composite material; Wherein, when rotary-jet, first MEDIA FLOW be looped around second MEDIA FLOW around, and the direction of rotation of first MEDIA FLOW is opposite with the direction of rotation of second MEDIA FLOW.
2. method according to claim 1, wherein, the Mach 2 ship 0.2-0.8 of the jet velocity of described first MEDIA FLOW, the rotary speed of described first MEDIA FLOW is 2000-10000 rev/min; The Mach 2 ship 1-1.8 of the jet velocity of described second MEDIA FLOW, the rotary speed of described second MEDIA FLOW is 2000-10000 rev/min.
3. method according to claim 2, wherein, the Mach 2 ship 0.5-0.8 of the jet velocity of described first MEDIA FLOW, the rotary speed of described first MEDIA FLOW is 4000-8000 rev/min; The Mach 2 ship 1-1.5 of the jet velocity of described second MEDIA FLOW, the rotary speed of described second MEDIA FLOW is 4000-8000 rev/min.
4. method according to claim 1, wherein, the mean particle diameter of described positive active material particle is the 1-200 micron.
5. method according to claim 1, wherein, with respect to the positive active material of 100 weight portions, the consumption of described clad material presoma is the 0.1-25 weight portion.
6. method according to claim 1 or 5, wherein, described clad material presoma is non-noble metal oxide presoma and/or silicon dioxide presoma.
7. according to claim 1,4 or 5 described methods, wherein, described positive active material is one or more in lithium cobalt oxygen, lithium nickel oxygen, lithium manganese oxygen, lithium nickel cobalt manganese oxygen and the LiFePO4.
8. method according to claim 1, wherein, the temperature of described sintering is 400-600 ℃, the time of described sintering is 200-400 minute.
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| CN102456929B (en) * | 2011-07-20 | 2014-10-08 | 宁波大学 | Method for manufacturing lithium iron phosphate all-solid-state film cell by in-situ spray pyrolysis |
| DE102016217372A1 (en) | 2016-09-13 | 2018-03-15 | Robert Bosch Gmbh | Process for producing a fibrillated material composition |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1372338A (en) * | 2001-02-28 | 2002-10-02 | 李许明 | Process for preparing spherical nano crystal lightium nickel cobaltate for lihtium secondary cell |
| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
-
2007
- 2007-12-19 CN CN200710300671XA patent/CN101465418B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1372338A (en) * | 2001-02-28 | 2002-10-02 | 李许明 | Process for preparing spherical nano crystal lightium nickel cobaltate for lihtium secondary cell |
| CN1872702A (en) * | 2006-06-16 | 2006-12-06 | 南京航空航天大学 | Method for preparing spinel type lithium manganate in use for material of positive pole in lithium ion battery |
Non-Patent Citations (1)
| Title |
|---|
| JP特开2001-79377A 2001.03.27 |
Cited By (4)
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|---|---|---|---|---|
| CN102709556A (en) * | 2012-06-04 | 2012-10-03 | 清华大学 | Spherical ultrafine iron phosphate preparation method |
| CN102709556B (en) * | 2012-06-04 | 2014-06-18 | 清华大学 | Spherical ultrafine iron phosphate preparation method |
| CN106861569A (en) * | 2017-04-28 | 2017-06-20 | 南京林业大学 | A kind of utilization gas prepares the preparation method and device of microballoon |
| CN106861569B (en) * | 2017-04-28 | 2019-10-11 | 南京林业大学 | A kind of preparation method and device preparing microballoon using gas |
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