Patent Application
20230307785
The invention relates to a separator for lithium ion battery.
Separator is a kind of polymer (such as polyolefin) membrane which is inserted between cathode electrode and anode electrode to prevent short circuit while permitting ionic conductivity via the electrolyte in lithium ion battery. It is important that the separator has good thermal resistance, mechanical strength and dimensional stability during operation of battery in order to comply with safety requirements.
U.S. Pat. No. 6,432,586 B1 discloses a separator having a ceramic composite layer on top of a polymeric microporous layer, especially for high energy rechargeable lithium battery. The manufacturing process of this ceramic composite layer involves very precious control of coating thickness. The ceramic fillers involved include SiO2, Al2O3, TiO2 and other materials. Embodiments of this patent disclose compositions comprising 60 parts of CaCO3 and 40 parts of PVDF:HFP, or 30 parts of SiO2 and 30 parts of CaCO3 with 40 parts of PVDF:HFP as components of the coating layer. The function of this coating layer is to block dendrite growth and to prevent electronic shorting.
In industrial applications, the same concept is also applied with even higher filler loading (90-95 wt. %) of fine particles of Al2O3 with small amount of binder as the composition of the coating layer, to block dendrite growth as well as to keep dimensional stability at higher temperature while still maintaining a good ionic conductivity. However, since the coating layer is a ceramic-rich composition, it is a common problem that ceramic particles fall off from the surface of the microporous polymeric substrate. The coating layers also add up to the total thickness of the separator and hence not only increase the production cost but also increase the total thickness of the lithium battery cell.
U.S. Pat. No. 6,949,315 B1 discloses a separator having good thermal shutdown performance while keeping improved mechanical properties. The manufacturing method comprises mixing a filler (TiO2 or SiO2) and a polymer with a plasticizer oil and extruding the mixture at high temperature in a twin-screw extruder, calendering the sheet, and removing the oil by solvent extraction (so-called wet process). The extraction step is followed by stretching and heat setting. Particle size of TiO2 mentioned is less than 0.2 μm. The filler is mixed with oil for easier handling process. The loading of the filler of typically 1 wt. % to 6 wt. % is not sufficient for achieving a good reinforcement. Using a solvent extraction step is not desired in view of its overall negative environmental impact and increased production cost. Therefore, it is necessary to develop an environmentally friendly solution.
US 2012/0145468 A1 discloses various lithium ion battery separators, made by biaxial stretching, having relevantly high filler loading ranging from 50 wt. % to 70 wt. %, in ultra-high molecular weight polyethylene (UHMWPE) with crosslinkable polyethylene (PE) using also plasticizer or process oil for incorporating ceramic fillers. Examples of filler used in this patent include AEROXIDE® Alu C, SpectaAl® 100, SIPERNAT® D 10, Hi-Sil® SBG. The results show the improvement of electric resistance of separators by all above mentioned fillers compared to those without fillers.
U.S. Pat. No. 8,003,204 B2 discloses a multi-layer separator with outer layer polypropylene (PP) containing a heat-resistant filler within inner polyethylene (PE) layer to have both a thermal shutdown function (contributed by low melting temperature of PE) as well as thermal resistance (contributed by thermal-resistant filler in PP). During the manufacturing process, pores are created in the polyolefin membrane at the interface between the filler and the PP matrix. All mentioned in this patent fillers are mostly in micrometer size, hence the contact area of the filler with the PP matrix should be limited and adhesion of the filler with the matrix should be reduced. Therefore, the reported content of the thermal-resistant filler is quite high, ranging from 30 wt. % to 80 wt. %, to achieve the desired performance. Moreover, the fixing of the filler in the PP matrix may be not optimal since crack exists at the interface. With too high content of the filler, the polyolefin loses its flexibility which is important for assembly process of lithium ion battery cell.
Therefore, it is desirable to develop an environmentally friendly separator preparation process which eliminates the need of using plasticizer oil, solvent or process oil and which provides a separator with good mechanical stability, flexibility, good overall electrochemical and safety performance including good thermal resistance, minimum dendrite growth and minimum tendency to electrical shorting.
The objective of the invention is to overcome at least part of the deficiencies of the prior art. The inventors surprisingly found that surface treated fillers can be uniformly incorporated with a reasonable percentage into a polymer (such as a polyolefin) matrix by dry mixing process without use of any plasticizer oil, solvent or process oil, particularly by twin-screw compounding, to make a masterbatch containing the filler. Then the masterbatch can be extruded to make a cast film, which is then stretched with well controlled crystalline temperature of the polymer. Hence pores are generated by different crystalline phase, to make a porous separator. In the present invention, the pores are generated within the whole polymer matrix (similarly to the pores formed in a pure polymer membrane), which is very different from prior art where pores are generated at the interface between the filler and the polymer. Furthermore, the filler has surface treatment to increase its affinity to the polymer matrix. Therefore, the filler can be efficiently integrated in the polymer matrix, which can significantly contribute to the improvement of the mechanical properties and thermal resistance. Even more surprisingly, when used as a separator of lithium ion batteries, the membrane prepared according to the dry mixing process of the invention presents superior performance such as electrochemical performance and safety performance, compared with membranes prepared by conventional wet process.
The invention provides a method to prepare a porous membrane suitable for use as a separator of a lithium ion battery, comprising the following steps:
The polymer and hydrophobic filler may be compounded at one time; thus it is not necessary to add hydrophobic filler in multiple times or batches. The polymer and hydrophobic filler may also be compounded at two or more times.
Compared with processes of prior art, the inventive process does not require any additional layer to be combined with the membrane nor any lamination steps. The porous membrane prepared according to the process of the invention is a monolayer membrane that can be directly used as a separator.
The invention further provides a porous membrane suitable for use as a separator of a lithium ion battery, prepared according to the method of the invention.
The invention further provides a porous membrane suitable for use as a separator of a lithium ion battery, which comprises a polymer matrix and a hydrophobic filler, wherein the hydrophobic filler is substantially uniformly distributed in the polymer matrix, and the amount of the hydrophobic filler is from 5% to 40% by weight, preferably 10%-30% by weight, based on the total weight of the polymer matrix and the filler.
One prominent advantage of the porous membrane of the invention is that the membrane can be a monolayer membrane that can be directly used as a separator, which is very different from the membranes of prior art which have two or more layers. Furthermore, compared with the membranes prepared by wet process, in the membrane of the invention, the hydrophobic filler is substantially uniformly distributed in the polymer matrix. The problem that filler particles fall off from the surface of the microporous polymeric substrate is also successfully solved. The membrane has significantly improved mechanical properties and thermal resistance.
The invention further provides a separator for a lithium ion battery, comprising the porous membrane according to the invention.
The invention further provides a lithium ion battery, comprising the separator according to the invention.
The invention further provides a device, comprising the lithium ion battery according to the invention. The device includes but not limited to, electric vehicles, electric home appliances, electric tools, portable communication devices such as mobile phones, consumer electronic products, and any other products that are suitable to incorporate the lithium ion battery of the invention as an energy source.
The method of the invention is a dry process or a dry mixing process, which is different from the wet process of prior art. In the method of the invention, the term “dry process” or “dry mixing process” refers to a mixing process that except polymers in liquid state compounded with hydrophobic filler, no liquid, including organic or inorganic liquid, such as diluent, plasticizer or solvent including but not limited to water, oil (such as process oil) or alcohol is required. Preferably, except polymers in liquid state compounded with hydrophobic filler, the method of the invention does not comprise using any liquid. If any other liquid is used, the amount of the liquid is preferably below 50% by weight, for example, below 40 wt. %, 30 wt. %, 20 wt. %, or 15 wt. %, more preferably below 10 wt. %, for example, below 9 wt. %, 8 wt. %, 7 wt. %, 6 wt. %, 5 wt. %, 4 wt. %, 3 wt. %, 2 wt. %, or 1.5 wt. %, even more preferably below 1 wt. %, for example, below 0.9 wt. %, 0.8 wt. %, 0.7 wt. %, 0.6 wt. %, 0.5 wt. %, 0.4 wt. %, 0.3 wt. %, 0.2 wt. %, or 0.1 wt. %, most preferably below 0.1 wt. %, for example, below 0.09 wt. %, 0.08 wt. %, 0.07 wt. %, 0.06 wt. %, 0.05 wt. %, 0.04 wt. %, 0.03 wt. %, 0.02 wt. %, or 0.01 wt. %, based on the total weight of the polymer and the filler.
The method of the invention does not need to use any plasticizer or plasticizer oil.
Plasticizer or plasticizer oil is used in prior art methods when mixing and/or extruding the filler and polymer. Preferably, no plasticizer or plasticizer oil is used in the method of the invention. Therefore, the present method is more environmentally friendly and more cost effective.
The method of the invention does not need to use any resin that may be required in prior art.
Therefore, the present method preferably does not use any resin except for the polymers compounded with the hydrophobic filler.
In fact, the method of the invention may use only the polymer and the hydrophobic filler as materials to prepare the porous membrane suitable for use as a separator of a lithium ion battery. Therefore, the inventive method preferably does not use any other material other than the polymer and the hydrophobic filler. Accordingly, the prepared porous membrane may consist of the polymer and the hydrophobic filler.
Polymer
The polymer is preferably selected from polyolefin, polyamide (PA), polyethylene terephthalate (PET) and polyimide (PI). The polyolefin may be selected from polyethylene, polypropylene (PP), polyisobutylene (PIB), poly-1-butene (PB), copolymers of ethylene and propylene (EP), and copolymers of ethylene and alpha olefins. The polyethylene is preferably selected from high-density polyethylene (HDPE) and ultrahigh molecular weight polyethylene (UHMWPE), especially HDPE, for example, HDPE F04660 commercially available from SABIC.
The hydrophobic filler is preferably nano-structured metal oxides. Preferably, the hydrophobic filler is selected from hydrophobic surface treated metal oxides such as alumina, ZrO2, MgO and ZnO, and the mixtures thereof, especially alumina. In some examples, the alumina is AEROXIDE® Alu C 805, commercially available from Evonik Operations GmbH. Silica or titanium dioxide are preferably not used due to their adverse effects to some aspects of the performance of lithium ion batteries. Thus, the hydrophobic filler of the invention preferably does not include silica and titanium oxide, or even fillers other than alumina.
The hydrophobic surface treated alumina is preferably selected from the pyrogenically prepared, surface modified aluminum oxide, especially alkyl silane modified aluminum oxide.
Particularly, the hydrophobic surface treated alumina is a pyrogenically prepared, surface modified aluminum oxide, having the following physical chemical properties:
Preferably, the hydrophobic surface treated alumina has been treated with a surface modification agent which is selected from the group consisting of:
More preferably, the hydrophobic surface treated alumina has been treated with a surface modification agent which is selected from the group consisting of:
Examples of such surface modification agent may include, octyltrimethoxysilane, oxtyltriethoxysilane, dimethyldichlorosilane, hexamethyldisilazane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dimethylpolysiloxane, glycidyloxypropyltrimethoxysilane, glycidyloxypropyltriethoxysilane, tridecafluorooctyltrimethoxysilane, aminopropyltriethoxysilane, or mixtures thereof.
The amount of the hydrophobic filler may be from 5% to 40% by weight, preferably, 10%-30% by weight, based on the total weight of the polymer and the filler.
In the compounding step, when a twin-screw extruder with at least one side feeder is used, it may be important that the screw rotation speed is from 100 rpm to 1000 rpm, preferably 200 rpm to 500 rpm.
In the compounding step, it may be important that the compounding is carried out in a twin-screw extruder with at least one side feeder. Two or more side feeders may also be used in the invention.
The compounding temperature may be in the range of 220° C.-260° C. The length/diameter ratio may be in the range of 30-60. Based on the description, a person skilled in the art can know and adjust the other settings and conditions of the compounding step or extruder operation to prepare a suitable compounded mixture applicable in the invention.
The compounding step can be carried out by a twin-screw extruder equipped with at least one side feeder, with a rotation speed of 200 rpm-500 rpm, length/diameter ratio in the range of 30-60, temperature of extruder barrels set at 220° C.-260° C. The masterbatch can contain 20% by weight or more of alumina.
The compounded mixture can be prepared as a masterbatch.
In the extruding and stretching step, the condition of extruding may be conventional, and the condition of stretching may be also conventional.
The cast films can be prepared using a lab scale cast film unit equipped with a 1.0 mm opening and 28 cm width slit die and two cooling drums.
The extrusion can be carried out at around 220° C. and the distance between the die exit to the nip roll of around 10 cm. The die temperature can be set at 220° C.
The stretching can be carried out on a biaxial stretching machine.
In the stretching step, the cast film can be
Extension ratio=(L1−L0)/L0*100%
Relaxation ratio is defined as the ratio of the difference between the original length (L0) and the obtained shrunk length (L2) versus the original length (L0):
Relaxation ratio=(L2−L0)/L0
The membrane of the invention has various advantages when used as a separator, such as, superior mechanical property, superior electrochemical property such as Gurley value and AC impedance, superior thermal shrinkage performance, good wettability of electrolyte on the surface of separator, good capacity performance, and, most importantly, excellent safety performance.
Furthermore, when used as a separator, the membrane of the invention has a comparable or even better performance than the separator with coatings in prior art. This may reduce the steps and cost of separator production.
Therefore, the inventive method enables preparation of a porous membrane suitable for use as a separator of a lithium ion battery without use of any plasticizer oil, solvent or process oil, using a suitable amount of a filler. Such prepared separator has superior performance such as mechanical strength and safety performance for lithium ion battery application.
Other advantages of the present invention would be apparent for a person skilled in the art upon reading the specification.
The invention is now described in detail by the following examples. The scope of the invention should not be limited to the embodiments of the examples.
Hydrophobic and hydrophilic alumina A twin-screw extruder (Coperion, Werner & Pfleiderer ZSK 30, Germany) was used to incorporate nano-structured alumina into polyethylene (PE) to make a PE masterbatch. In order to achieve targeting reinforcement, the filler content in the embodiment was 20 wt. %.
During masterbatch preparation process, the sieving pressure over time was monitored as an indication of dispersibility of nano-structured alumina in high density polyethylene (HDPE F04660, SABIC). As shown in
In the following embodiments, the preferred nano-structured alumina was therefore the hydrophobic one, AEROXIDE® Alu C 805.
In the following examples, the performance of separators made from the inventive membrane were compared with the commercial pure PE separator (Comparative Example 1), commercial filler-containing PE separator made by wet process (Comparative Example 2), and commercial filler-containing PE separator made by wet process with a further filler coating (Comparative Example 3). The separators made from the inventive membrane showed surprisingly superior performance, especially safety performance.
In order to achieve 20 wt. % filler loading in HDPE, the compounding HDPE F04660 AEROXIDE® Alu C 805 was carried out in a twin-screw extruder (Coperion, Werner & Pfleiderer ZSK 30, Germany) equipped with one side feeder in two extrusion steps (each extrusion step incorporating half amount of the alumina), with a screw speed of 280 rpm, length/diameter ratio of 36, temperature of extruder barrels set with decreasing temperature profile setting down the melt stream, 240° C. for first extruder barrel after main hopper, then decrease to 200° C. for last extruder barrel before die head. Recorded melt temperature in the die head was 223° C. 900 g alumina was added through the side feeder and compounded with 8100 g HDPE F04660 in the first extrusion step to achieve 10 wt. % filler loading.
A second extrusion steps was applied to achieve 20 wt. % loading of AEROXIDE® Alu C 805 (each extrusion step 10 wt. %): 7200 g of the compounded mixture obtained above was fed into the extruder again and further compounded with 900 g AEROXIDE® Alu C 805 added through the side feeder according to the same procedure above. Then a PE masterbatch containing 20 wt. % AEROXIDE® Alu C 805 was obtained.
The PE masterbatch was firstly extruded to obtain cast films and then the cast films were stretched to prepare porous membranes. Using the above prepared PE masterbatch, the cast films were prepared using a lab scale cast film unit from Leistritz equipped with a 1.0 mm opening and 28 cm width slit die and two cooling drums.
The extrusion of the PE masterbatch was carried out at 220° C. and the distance between the die exit to the nip roll was 10 cm. The die temperature was set at 220° C. After this step, the cast film for stretching was obtained.
The stretching was then carried out on a biaxial stretching machine (Toyo Seiki). The cast film was firstly annealed at 120° C. for 30 minutes, and then extended with 40% ratio with 3000 mm/min at room temperature. It was then heated up to 120° C. in 20 minutes and extended 60% ratio with 10 mm/min at 120° C., followed by a heat setting at 120° C. for 5% relaxation, and kept at 120° C. for 10 minutes and then cooled down to room temperature. Then a porous membrane was obtained.
The porous membrane was used for measurement of physical/chemical/mechanical performance and as separator for lithium ion battery cell assembly.
A porous membrane was prepared based on a commercially purchased HDPE F04660. The membrane was prepared according to the same extrusion and stretching methods as in Example 1 using the HDPE F04660.
A commercial PE separator ND-416 Z from Asahi Kasei (with UHMWPE) made by wet process was purchased and used as separator of Comparative Example 2.
The ND-416 Z separator was used as base substrate for further coating, with a ceramic coating formulation: “AERODISP®W 450 ZX” (which is a water based dispersion comprising 50 wt. % of fumed alumina, commercially available from Evonik Operations GmbH, Germany), and acrylic type of binder TRD202A (from JSR, Japan), with a weight ratio of fumed alumina:binder=20:1. The coating was performed with a slot-die coating machine (“Easycoater EC58” from Coatema Coating Machinery GmbH, Germany), with coating speed of slot-die at 0.4 m/min and flow rate at 0.8 ml/min, followed by drying at 50° C. for 2 hours. A single side coated separator with a final dry coating layer having a thickness of 2 μm was obtained.
Pore Morphology of the Separators
The pore morphology of the separators was examined under a scanning electron microscope. As shown in
Mechanical Property of Separators
In order to check the mechanical properties of obtained separators, tensile strength and elongation were measured by a universal tensile test machine (Hung Ta Instrument Co., Ltd., Taiwan), based on ASTM D882 standard. From the results as shown in Table 1, it can be seen that by adding AEROXIDE® Alu C 805, the tensile strength was improved by 14%, while the elongation was improved by 28%, compared to the intrinsic HDPE. If further comparing the results with those of Asahi Kasei's commercial separator, the compounded separator also outperformed in this regard, showing that a good mechanical reinforcement by nano-structured alumina was obtained. This shows that the inventive separator made by dry process has superior mechanical property than the separator of prior art made by wet process.
Gurley Value and AC Impedance of Separators
Gurley value is a measurement of time for air flow through porous membrane, which is an indication for flowability of liquid electrolyte, representing electrical conductivity of the separator. The measurement was done by a Gurley meter with 10 cc air flow, based on ASTM D726-58. AC impedance of the separator can further be measured by inserting separator between two stainless plates, filling the electrolyte into the gaps, then applying a voltage at 3.6 V at 0.1-100000 Hz to the stainless plates. The latter result is more relevant to the performance in lithium ion battery.
The results are shown in Table 2. Despite Asahi Kasei's PE separator had lowest Gurley value and AC impedance, the influence of thickness on Gurley value and AC impedance cannot be ignored. Therefore, the measured value was further normalized by thickness of the test specimen to obtain the normalized results as shown in Table 2. These results indicate that the separator with compounded AEROXIDE® Alu C 805 shows comparable Gurley value and better AC impedance to the commercial Asahi Kasei's PE separator made by wet process, while better performance compared with intrinsic properties of HDPE separator, showing excellent improvement by adding AEROXIDE® Alu C 805.
Contact Angle of Separators
Measurement of contact angle is an indicator of wettability of electrolyte on the surface of separator. From the results as shown in Table 3, all the three separators have comparable contact angle since the surface conditions are similar, with PE exposed to electrolyte.
Thermal Shrinkage of Separators
Thermal shrinkage of different separators at high temperature at 110° C. and 125° C., respectively, were tested. The test was set based on ASTM 1204-94 standard. Separators with pre-determined area with 5 cm×5 cm were fixed between two papers at four ends to prevents rolling up during the elevated temperatures and put in the oven heated up at selected temperature for 0.5 hours, taken out for dimensional check. The percentage shown was measured along MD direction. The results were summarized in Table 4 below.
PE tends to shrink at high temperature, once it has shrunk, it will lose the functionality of separator (separating cathode and anode), leading to short circuit. As shown in Table 4, the inventive compounded separator has superior thermal shrinkage compared with separator of prior art made by wet process, which is very important for achieving safety performance of LiB operated at high temperature.
However, this is only static demonstration in terms of safety performance, since most of the lithium ion batteries will not be operated at so high temperature. Instead, failed batteries may be found during operation. Thus, the test methods with dynamic simulation just like the battery operation is still necessary to further determine the performance of the separator.
Performance Test in a Real Lithium Ion Battery
In order to check the real performance of the invented separator, it is necessary to assemble the separator in a real lithium ion battery for further tests. The designed platform for this test is a 2.5 Ah pouch cell with cathode NCM 811 (a cathode composition with 80% nickel, 10% manganese, and 10% cobalt), commercial graphite as anode and 1M LiPF6 in EC/EMC/DMC (ethylene carbonate+dimethyl carbonate+ethylmethyl carbonate, 1:1:1 vol. %) solvent as the electrolyte. Separators selected in the following tests included the blank separator according to Comparative Example 1 (made of HDPE F04660 only), the inventive separator according to Example 1 (made of HDPE F04660 compounded with 20 wt. % AEROXIDE® Alu C 805), benchmark PE separator according to Comparative Example 2 (Asahi Kasei's ND-416Z made by wet process) and coated PE separator according to Comparative Example 3 (ND-416 Z with single side 2 μm coating with AEROXIDE® Alu 65). Cathode electrodes were prepared by mixing NMC811, carbon black (Super P), PVDF binder and oxalic acid in a weight ratio of 94.9:3:2:0.1. The slurries were coated on aluminum current collectors via a slot-die coater and dried in a continuous oven at 110° C. Anode electrodes were prepared by mixing commercial graphite (MG11-A, commercially available from China Steel Chemical Corporation, Taiwan), carbon black (Super P), synthetic graphite (TIMCAL TIMREX® KS6 Primary Synthetic Graphite), styrene-butadiene rubber (SBR) and carboxymethyl cellulose (CMC) in a weight ratio of 92.2:1:3:2:1.8. The slurries were coated on copper current collectors via slot-die coater and dried in a continuous oven at 90° C. After the coating process, cathode and anode electrode were calendared into proper thickness. The density of the cathode/anode electrode were 3.25 g/cm3 and 1.65 g/cm3 respectively. Then the electrodes were slit into proper size for 2.5 Ah pouch cell, with 55 mm*82 mm for cathode and 57 mm*84 mm for anode in rectangle shape.
Cell assembling steps in the tests described were as follows:
Electrochemical Performance Test
In capacity check, the batteries were charged up to a cell voltage of 4.2 V followed by a taper charge of this potential (4.2 V) with a cut-off current of 40 mA. The discharge current kept the same current down to a cut-off voltage of 2.8 V. All charge-discharge cycling tests and performance tests were conducted with a battery test system (MACCOR SERIES 4000 AUTOMATED, MACCOR, Inc., Oklahoma, USA) at room temperature. The C-rate test can check the discharge power ability of LIBs. The cell discharged from 4.2V to 2.8V with different C-rate current such as 0.2 C, 0.5 C, 1 C and 2 C. The discharge capacity was represented as the retention rate of the initial 0.2 C discharge capacity. Cycle life test indicated the reliability of the lithium ion batteries. The lithium ion batteries charged & discharged with 1 C current and the voltage interval was 2.8V-4.2V.
As shown in Table 5, the inventive separator has much superior electrochemical performance (in terms of capacity retention discharging at 1 C, 2 C and cycling for 200 cycles) compared to Comparative Example 1 (F04660), and comparable to those of Comparative Examples 2 and 3.
Safety Performance Evaluation
Safety performance evaluation includes nail penetration test via a nail penetration tester and overcharge test.
Nail Penetration Test
The nail penetration is a method that provides an internal short circuit scenario and evaluate the safety of the cell. The set-up was based on a safety chamber with good gas exhaust and fire protection, and most importantly with a motor controlled moving tip. During the test, some sensors were attached on/with a battery and record the temperature/voltage change during penetration. In the test, the most severe conditions were chosen to distinguish the safety performance of various separators in pouch cell. Type of nail selected was glass fiber with 3 mm diameter, which simulated severe internal short circuit scenario since it was easier to accumulate heat with glass fiber tip compared to metallic ones. Nail speed was set at 1 mm/sec. Voltage drop was set at 70 mV for partial penetration to identify the safety of the cell. Once the voltage drop exceeded 70 mV, the nail would stop penetrating and hold for 5 minutes. If the separator could not stop the voltage leak, voltage would keep dropping and cause energy releasing. With heat accumulating, the cell would go thermal runway eventually. On the other hand, if the separator stopped the voltage leak during the test, cell could hold the voltage and prevent thermal runway.
As shown in
To further compare the safety performance of compounded and coated separators, voltage drop during nail penetration was set at higher level at 80 mV. As shown in
Overcharge Test
Overcharge test is another method to evaluate the safety performance of the cell with abnormal charging process. In the test, lithium ions keep leaving from cathode material and at the end the cathode structure will start collapse. Once cathode collapses, it triggers a chain reaction such as heat/gas generation, electrolyte decomposition, internal short circuit and thermal runway.
In this test, cell was fully charged first and then started charge to 6V with 1 C current for 1 hour. During the overcharge test, heat and gas generation would deform the shape of the cells and the separators got shrinkage. As shown in
Puncture Test and Hot Tip Test on Separators
In order to know more about the mechanism why the reinforced separators could outperform in safety tests, the evaluation of puncture test and hot tip test on separators was carried out. Puncture test with tip penetrating separator which has fixed on metal carrier can determine the resistance to penetration, either from internal forming lithium dendrite or external mechanical impact force, during battery storage. Hop tip test with heated tip penetrating fixed separators can even further explain the dynamic resistance of separators to applied force at high temperature, simulating the resistance of separators to the penetration during battery operation.
Set-up for puncture test was designed based on ASTM D5748 standard. Tested separator, which had been fixed on the stainless fixture, had 3 mm in radius. Speed of tip was set at 50 mm/min. The loadcell equipped on top of tip recorded the force until the separator was broken. This test could simulate the mechanical resistance, to external impact or lithium dendrite inside LiB cell, of separator during static application condition such as storage or transportation of lithium battery. Set-up for hot tip test was the same as puncture test, but using the tip which could be heated at a constant temperature. In the test, the temperature of tip was set at 120° C. The tip speed was set at 20 mm/min, with a fixed penetration depth at 1.5 mm (taking the position where tip touches the separator as zero point), and the force change was recorded for 120 seconds. Hot tip test can simulate the mechanical resistance, to external impact or lithium dendrite inside LiB cell, of separator during dynamic application condition such as charging or discharging of lithium battery.
Despite the force at the broken of compounded separator was inferior to others, this was more relevant to the static situation so it is better to check the performance at pre-determined displacement to simulate the application. In this case, the force with fixed 2 mm depth penetration was checked. It was surprisingly found that the compounded separator according to Example 1 had comparable result compared to coated separator according to Comparative Example 3 and outperformed to HDPE separator according to Comparative Example 1 and Asahi Kasei's separator according to Comparative Example 2. As mentioned above, the hot tip test was used to simulate the dynamic situation, so the response versus time also needed to be considered. In the measurement, the inventors continuously recorded the force during the test period and checked the time when the force decayed to half, which represented resistance to external impact during operation.
From the results, it was surprisingly found that the length of time of compounded separator was 40% higher than those of Asahi Kasei's separator according to Comparative Example 2 and coated separator according to Comparative Example 3 and was even 250% of the blank separator according to Comparative Example 1. This shows that the nano-structured alumina reinforced separator of the invention has excellent mechanical resistance to external impact or internal lithium dendrite for both static and dynamic conditions.
The overall performance of various separators in puncture tests and hop tip test were summarized in Table 7 below.
As used herein, terms such as “comprise(s)” and the like as used herein are open terms meaning ‘including at least’ unless otherwise specifically noted.
All references, tests, standards, documents, publications, etc. mentioned herein are incorporated herein by reference. Where a numerical limit or range is stated, the endpoints are included. Also, all values and subranges within a numerical limit or range are specifically included as if explicitly written out.
The above description is presented to enable a person skilled in the art to make and use the invention and is provided in the context of a particular application and its requirements. Various modifications to the preferred embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments and applications without departing from the spirit and scope of the invention. Thus, this invention is not intended to be limited to the embodiments shown but is to be accorded the widest scope consistent with the principles and features disclosed herein. In this regard, certain embodiments within the invention may not show every benefit of the invention, considered broadly.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20185989.9 | Jul 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/068499 | 7/5/2021 | WO |
