CN117832649A - Cylindrical battery winding core with high energy density design and cylindrical battery - Google Patents
Cylindrical battery winding core with high energy density design and cylindrical battery Download PDFInfo
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- CN117832649A CN117832649A CN202410242786.1A CN202410242786A CN117832649A CN 117832649 A CN117832649 A CN 117832649A CN 202410242786 A CN202410242786 A CN 202410242786A CN 117832649 A CN117832649 A CN 117832649A
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- high energy
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- 238000013461 design Methods 0.000 title claims abstract description 14
- 238000004804 winding Methods 0.000 title description 23
- 239000000945 filler Substances 0.000 claims abstract description 53
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 34
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 34
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 29
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 15
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000002861 polymer material Substances 0.000 claims abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 238000007599 discharging Methods 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000007600 charging Methods 0.000 claims description 5
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 4
- 238000001125 extrusion Methods 0.000 claims description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical group [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 238000005562 fading Methods 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 23
- 238000000034 method Methods 0.000 abstract description 21
- 230000008569 process Effects 0.000 abstract description 10
- 238000005338 heat storage Methods 0.000 abstract description 9
- 230000008093 supporting effect Effects 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 15
- 238000011049 filling Methods 0.000 description 15
- 239000007789 gas Substances 0.000 description 12
- 238000003860 storage Methods 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000003466 welding Methods 0.000 description 7
- 238000010280 constant potential charging Methods 0.000 description 6
- 238000010277 constant-current charging Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 229910021383 artificial graphite Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- SOCJEFTZDJUXNO-UHFFFAOYSA-L lithium squarate Chemical compound [Li+].[Li+].[O-]C1=C([O-])C(=O)C1=O SOCJEFTZDJUXNO-UHFFFAOYSA-L 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
The invention belongs to the technical field of lithium ion batteries, and discloses a cylindrical battery roll core with high energy density design and a cylindrical battery, wherein the cylindrical battery roll core comprises: the lithium ion battery comprises a positive plate, a negative plate and a diaphragm, wherein the positive plate is separated from the negative plate through the diaphragm, the positive plate, the negative plate and the diaphragm are wound to form a hollow cylinder structure, a central hole is formed in the hollow cylinder structure, and a filler is filled in the central hole and is a mixture of lithium salt, carbon materials and high polymer materials. Through mixing lithium salt, carbon material and macromolecular material, further promoted the mechanical strength of book core, strengthened the supporting effect, improved mechanical stability to lithium salt can also carry out lithium replenishment after the active lithium consumption of battery cycle process, thereby promotes cycle performance. When the lithium salt is consumed, the remaining porous structure can store gas, so that the quantity of the heat storage gas is further reduced, and the heat storage safety performance, particularly the heat storage performance after circulation, is improved.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a cylindrical battery winding core with high energy density design and a cylindrical battery.
Background
The lithium ion battery is a common energy storage device and can be used in various application scenes such as vehicles, mobile phones, electric tools, energy storage power stations and the like and provide energy. With the continuous increase of the energy and capacity requirements of lithium ion batteries, the size of the cylindrical battery is gradually increased, and the energy density per unit volume or weight is continuously increased. With the improvement of lithium ion energy density, larger volume changes can occur in particles, pole pieces, winding cores and the like in the lithium ion battery, but the volume changes can reduce the stability of the structures of the pole pieces and the winding cores of the cylindrical battery, and a series of problems such as local deformation, winding core collapse, diaphragm puncture, positive and negative electrode short circuit and the like are easy to occur, so that the battery short circuit is caused, and the safety problem is caused. Furthermore, the center of a common cylindrical battery is hollow, and in this case, stresses caused by expansion of active materials and pole pieces are preferentially released at the center, especially at the tail end of the positive electrode, and are very likely to be points at which deformation starts. Aiming at the problems, the existing treatment mode is to fill a hard material in the central hole of the cylindrical battery of the battery to improve the structural stability of the cylindrical battery, and the design of the central supporting structure adopts a mode of matching a hard central needle with polymer injection or directly adopts the polymer injection, so that the problem of structural collapse of the cylindrical battery can be effectively solved. However, the solutions adopt organic matters to improve the performance independently, and the improvement effect is mainly reflected in single improvement of mechanical structure stability, and has no effect on the cycle performance and thermal energy storage of the battery.
Therefore, it is necessary to develop a cylindrical battery winding core and a cylindrical battery with high energy density design to solve the problems of poor stability of the central hole structure, low cycle performance of the battery, no heat energy storage effect, and the like.
Disclosure of Invention
The invention aims to provide a cylindrical battery winding core with high energy density design and a cylindrical battery.
The technical scheme of the invention is as follows:
a cylindrical battery core of high energy density design, comprising: the lithium ion battery comprises a positive plate, a negative plate and a diaphragm, wherein the positive plate is separated from the negative plate through the diaphragm, the positive plate, the negative plate and the diaphragm are wound to form a hollow cylinder structure, a central hole is formed in the hollow cylinder structure, and a filler is filled in the central hole and is a mixture of lithium salt, carbon material and high polymer material.
Further, the lithium salt is selected from lithium carbonate, lithium fluoride, lithium oxalate, li 2 NiO 2 Or any one of lithium squaratesOr a plurality thereof.
Further, the carbon material is selected from any one or two of porous carbon or carbon powder.
Further, the polymer material is selected from one or more of PP, PET, PI and PFA.
Further, if the ratio of the volume of the filler to the volume of the central hole is y, y is more than or equal to 0.4 and less than or equal to 0.8.
Further, if the mass percentage of lithium in the filler is a, a is more than or equal to 0.1% and less than or equal to 5%.
Further, the preparation method of the filler comprises the following steps:
(1) Fully stirring the lithium salt, the carbon material and the polymer material in a magnetic stirrer at the rotating speed of 200r/min for 6 hours, then putting the mixture into a baking oven with the temperature of 120 ℃ and adding the mixture into N 2 Maintaining for 10min under atmosphere to obtain a mixture;
(2) The mixture was charged into a twin screw extruder, extruded into the central bore at a rate of 5g/min using a 2.5mm extrusion head, and left at room temperature for 3 hours to form a charge.
Further, the mass ratio of the solid part of the filler to the mass of the substance in the central hole is 0.6-0.99.
Further, when the charge-discharge cycle is performed by 0.5C charge and 0.5C discharge, the relationship between the mass of the filler and the charge-discharge cycle is as follows: and (3) assuming that the mass percentage of lithium in the filler after 100 weeks of circulation is b, the mass percentage of lithium in the filler before circulation is a, and the capacity fading percentage after 100 weeks of circulation is x, a/b is less than or equal to 150x, wherein when x is less than 1%, the value of x is 1%.
The other technical scheme of the invention is as follows:
a cylindrical battery comprising a cylindrical battery core of high energy density design, said cylindrical battery having a diameter of 20-50mm and a height of 60-150mm.
The invention provides a cylindrical battery winding core with high energy density design and a cylindrical battery, which have the beneficial effects that:
functional filling is carried out at the central position of the cylindrical battery in a mode of combining lithium salt, carbon materials and high polymer materials, and the filling can provide structural support, so that the mechanical strength of the cylindrical battery is improved;
the filler at the central hole contains lithium salt, can be dissolved into the battery, and supplements new lithium after the cyclic decay;
after the lithium salt is dissolved, the filler structure at the central hole is changed into a porous structure, and the porous structure and inorganic matters in the filler can effectively adsorb gas generated at high temperature of the battery, so that the thermal storage stability after circulation is improved.
Detailed Description
The invention designs a cylindrical battery winding core with high energy density, which is formed by winding a positive plate, a negative plate and a diaphragm, wherein a hollow cylinder structure is formed in the center of the winding core, and a central hole is formed in the center of the hollow cylinder structure, so that the overall performance of the battery core can be improved by filling fillers. The positive plate can be one or more of lithium iron phosphate, ternary layered oxide, lithium cobalt oxide, lithium manganese iron phosphate, lithium nickel manganese oxide and lithium manganese oxide; the negative plate can be one or more of artificial graphite, natural graphite, hard carbon, soft carbon, porous carbon, silica, silicon carbon and silicon; the filler comprises at least one lithium salt, one carbon material and one organic material, wherein the lithium salt is selected from lithium carbonate, lithium fluoride, lithium oxalate and Li 2 NiO 2 Or any one or more of lithium squarate, the carbon material is selected from one or two of porous carbon or carbon powder, and the organic material is selected from any one or more of PP, PET, PI or PFA. The ratio y of the volume of the filler to the volume of the central hole satisfies that y is more than or equal to 0.4 and less than or equal to 0.8, and the mass percentage a of lithium in the filler satisfies that a is more than or equal to 0.1 and less than or equal to 5 percent. The filler is prepared by preheating lithium salt, carbon material and polymer material, extruding, and directly filling into the central hole. The mass of the filler occupies the mass of the solid portion of the material in the central bore in the range of 0.6-0.99; the following relationship is satisfied between the lithium content of the filler and the charge-discharge cycle: the charge of 0.5C and the discharge of 0.5C are adopted for circulation, after 100 weeks of circulation, the mass percentage b of lithium of the filling material and the mass percentage a of lithium before circulation satisfy that a/b is less than or equal to 150x, and x is 10Percent capacity fade at 0 week (1% when x is less than 1%).
The cylindrical battery winding core with the high energy density design can be used for a cylindrical battery. The cylindrical battery comprises a cylindrical battery winding core, a positive electrode bus plate, a negative electrode bus plate, an insulating plate, a shell and a cap, wherein the cylindrical battery winding core is designed with high energy density. The upper and lower ends of the cylindrical battery winding core designed with high energy density are respectively provided with a positive electrode lug and a negative electrode lug. The coil core is connected with the negative electrode bus bar through welding, the negative electrode bus bar is connected with the shell through welding, the coil core is connected with the positive electrode bus bar through welding, the insulating sheet is placed on the positive electrode bus bar, and the positive electrode bus bar is connected with the cap through welding. The cap is connected with the shell through the rolling groove. In the above structure, the tab may be a single, multiple tabs or a full tab, and the outer shell may be a steel shell or an aluminum shell. The diameter of the cylindrical battery is 20-50mm, and the height is 60-150mm.
In order to make the above objects, features and advantages of the present invention more comprehensible, the following embodiments accompanied with examples are further described. The invention is not limited to the embodiments listed but includes any other known modification within the scope of the claims that follow.
Reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic may be included in at least one implementation of the invention. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1 this embodiment shows a method for manufacturing a cylindrical battery with a cylindrical battery core designed with high energy density as follows.
1. And winding the positive plate, the negative plate and the diaphragm through a winding machine to form a winding core, and coating a layer of expansion adhesive tape on the outer ring.
2. Accurately weigh 423mg PET micro-rice flour, 100mg Li 2 NiO 2 And 20mg of carbon powder, stirring with a magnetic stirrer at 200r/min for 6 hr, placing into a box-type furnace, and adding into N 2 Atmosphere ofNext, the mixture was obtained by heating at 120℃for 10 minutes. The mixture was charged into a twin screw extruder, extruded into the central bore of the core using a 2.5mm extrusion head and at a rate of 5g/min, and left at room temperature for 3 hours to form the charge.
3. And cutting and stacking the positive electrode lug and the negative electrode lug on the coiled core filled with the filler, welding the positive electrode confluence sheet, the negative electrode confluence sheet and the coiled core respectively, welding the negative electrode confluence sheet and the steel shell, placing an insulating sheet above the positive electrode confluence sheet, and welding the positive electrode confluence sheet and the cap. And then finishing rolling groove, liquid injection, sealing and obtaining the cylindrical battery.
The relevant parameter settings involved in this embodiment are as follows in table 1:
TABLE 1
Example 2, this example is identical to example 1 except that the lithium salt is lithium carbonate and the mass percentage a of lithium in the filler is 3.5%.
Example 3 the same procedure as in example 1 is followed except that the lithium salt is lithium squarate and the mass percentage a of lithium in the filler is 1.0%.
Example 4 the same procedure as in example 1 is followed except that the lithium salt is lithium oxalate and the mass percentage a of lithium in the filler is 2.5%.
Example 5 this example is the same as example 1 except that the lithium salt is lithium fluoride and the mass percentage a of lithium in the filler is 5.0%.
Example 6 this example is identical to example 1 except that the PET weighs 443mg and no carbon powder is added.
Example 7 this example is identical to example 1 except that the carbon powder is replaced with porous carbon.
Example 8 this example is identical to example 1 except that PET is replaced with PP and the PP weight is 275mg and the heating conditions are changed to 200℃for 30min.
Example 9 this example is identical to example 1 except that PET is replaced with PFA and the PFA weight is 620mg and the heating conditions are changed to 280℃for 30min.
Example 10 this example is identical to example 1 except that the PET is replaced with PI and the PI weight is 425mg and the heating conditions are changed to 400℃for 30min.
Example 11, this example is identical to example 1 except that the ratio y of the volume of the filler to the volume of the central hole is 1.
Example 12, which is identical to the process of example 1, except that the ratio y of the volume of the filler to the volume of the central hole is 0.8.
Example 13, this example is identical to example 1, except that the ratio y of the volume of the filler to the volume of the central hole is 0.4.
Example 14, which is identical to the process of example 1, differs only in that the ratio y of the volume of the filler to the volume of the central hole is 0.1.
Example 15 the process is the same as that of example 1, except that Li 2 NiO 2 The addition amount of (2) was 18mg.
Example 16, which is identical to the process of example 1, except that Li 2 NiO 2 The amount of (2) added was 250mg.
Example 17 the process is the same as that of example 1, except that Li 2 NiO 2 The amount of (2) added was 3mg.
Example 18 this example is identical to example 1 except that the filling in step 2 is a cylindrical central needle of 3mm or less diameter prepared beforehand from the same quantity of material and inserted into the central hole.
Example 19 the method of example 1 is identical except that the filling in step 2 is a cylindrical central needle of diameter less than or equal to 2mm, which has been prepared from half the amount of material, is inserted into the central bore while the other half of the material is forced into the central bore.
Example 20 the procedure is the same as in example 1 except that the filling in step 2 is a cylindrical central needle of diameter less than or equal to 2.5mm, previously prepared from 80% pure PET material, inserted into the central bore while the remainder of the material is forced into the central bore.
Example 21 this example is identical to example 1 except that the PET weight is 270mg and the carbon powder weight is 12mg.
Example 22, which is identical to the process of example 1, except that Li 2 NiO 2 The weight of (2) was 30mg, the weight of PET was 480mg, and the weight of carbon powder was 60mg.
Example 23 this example is the same as example 1 except that the weight of PET is 10mg and the weight of carbon powder is 3mg.
Example 24, this example was identical to example 1 except that the battery type was replaced with 21700 monopolar ear.
Example 25, which is identical to example 1 except that the battery type is replaced with 4695 full tabs.
Example 26, which is identical to example 1 except that the battery type is replaced with 46120 full tab.
Example 27 the method is the same as example 1 except that the positive plate material is NCMA90 and the negative plate material is 85% artificial graphite +15% silicon carbon.
Example 28 the method of this example is the same as that of example 1 except that the positive electrode sheet material is lithium iron phosphate and the negative electrode sheet material is artificial graphite.
Example 29 the method of this example is the same as that of example 1 except that the positive electrode sheet material is lithium iron phosphate and the negative electrode sheet material is 97% artificial graphite +3% silicon carbon.
Example 30, which is identical to example 1, differs only in that the electrolyte injection amount is 6.3g.
Example 31, which is identical to example 1, differs only in that the electrolyte injection amount is 7.4g.
Comparative example 1
This comparative example is identical to the method of example 1, except that no filler is filled at the central hole.
Comparative example 2
This comparative example was identical to the process of example 1, except that no lithium salt was added.
Comparative example 3
This comparative example is identical to the process of example 1, except that the ratio y of the volume of the filler to the volume of the central hole is 0.05.
Comparative example 4
This comparative example is identical to example 1, except that Li 2 NiO 2 The addition amount of (2) was 1300mg.
Comparative example 5
This comparative example was the same as in example 1 except that the electrolyte injection amount was 7.8g.
The performance evaluation was performed with respect to the cylindrical batteries of examples 1 to 31 and comparative examples 1 to 5, and the evaluation method was as follows:
1. cycle performance and center hole collapse after cycle test (taking cylindrical battery test of high nickel and graphite mixed silicon cathode as an example, other types of batteries, the tested voltage interval needs to be corrected)
Taking a cylindrical battery, such as 21700 Ah, placing in a constant temperature box at 25 ℃ for more than 4 hours, and testing according to the following steps:
(1) Discharging the battery to 2.5V under the condition of 0.1C, and standing for 5min;
(2) Constant-current charging is carried out on the battery to 4.2V cut-off under the condition of 0.2C, constant-voltage charging is carried out to 0.05C cut-off, and standing is carried out for 5min;
(3) Discharging the battery under constant current at 0.2C to 2.5V cut-off, standing for 5min, and reading the capacity value C at the moment 0 ；
(4) Constant-current charging the battery to 4.2V under the condition of 1.0C, constant-voltage charging to 0.05C, stopping, and standing for 5min;
(5) Discharging the battery to 2.5V under the condition of 2.0 ℃ under constant current until the battery is cut off, and standing for 5min;
(6) Repeating the step (4) and the step (5) 600 times;
(7) And (3) obtaining the cycle performance, namely the capacity retention rate, of the single battery through the ratio of the 600 th discharge capacity to the 1 st discharge capacity of the step (4) and the step (5).
(8) Taking at least 5 circulated batteries, observing the deformation condition of the foil material of the central hole of the batteries under CT, requiring no obvious foil material deformation or collapse of the winding core to pass, and recording the passing rate.
If the positive electrode of the battery is lithium iron phosphate, the following test steps are changed:
a cylindrical battery, such as 21700 Ah, was placed in an incubator at 25℃for more than 4 hours and tested as follows:
(1) Discharging the battery to 2.0V under the condition of 0.1C, and standing for 5min;
(2) Constant-current charging is carried out on the battery to 3.6V cut-off under the condition of 0.2C, constant-voltage charging is carried out to 0.05C cut-off, and standing is carried out for 5min;
(3) Discharging the battery under constant current at 0.2C to 2.0V cut-off, standing for 5min, and reading the capacity value C at the moment 0 ；
(4) Constant-current charging the battery to 3.6V under the condition of 1.0C, constant-voltage charging to 0.05C, stopping, and standing for 5min;
(5) Constant-current discharging the battery to 2.0V under the condition of 1.0C, constant-current discharging to 2.5V, stopping, and standing for 5min;
(6) Repeating the step (4) and the step (5) for 2000 times;
(7) And (3) obtaining the cycle performance, namely the capacity retention rate, of the single battery through the ratio of the 2000 th discharge capacity to the 1 st discharge capacity of the step (4) and the step (5).
(8) Taking at least 5 circulated batteries, observing the deformation condition of the foil material of the central hole of the batteries under CT, requiring no obvious foil material deformation or collapse of the winding core to pass, and recording the passing rate.
2. Battery 130 ℃ heat storage and gas production test after circulation
One cell after 600 weeks of cycling was taken, placed in a incubator at 25 ℃ for more than 4 hours, and tested as follows:
(1) Discharging the battery to 2.5V under the condition of 0.1C, and standing for 5min;
(2) Constant-current charging is carried out on the battery to 4.2V cut-off under the condition of 0.2C, constant-voltage charging is carried out to 0.05C cut-off, and standing is carried out for 5min;
(3) Placing the battery into an incubator, setting the temperature rising rate to be 5K/min, rising the temperature to 130 ℃, keeping for 1h, stopping heating, and self-heating and cooling to below 30 ℃;
(4) The battery is not fired and smoked, and is considered to pass, otherwise, the battery is not passed, at least 5 batteries are tested, and the passing rate is recorded.
(5) After the test is completed, judging whether the CID of the battery is opened or not, and counting the cover opening rate.
If the positive electrode of the battery is lithium iron phosphate or lithium manganese iron phosphate, the temperature is raised from 130 ℃ to 140 ℃, and after the cycle number is 2000 weeks, the rest conditions are not changed.
3. 100 week cycle lithium content test
At least 3 cylindrical batteries, such as 21700 Ah, were placed in an incubator at 25℃for more than 4 hours and tested as follows:
(1) Discharging the battery to 2.5V under the condition of 0.1C, and standing for 5min;
(2) Constant-current charging is carried out on the battery to 4.2V cut-off under the condition of 0.2C, constant-voltage charging is carried out to 0.05C cut-off, and standing is carried out for 5min;
(3) Discharging the battery under constant current at 0.2C to 2.5V cut-off, standing for 5min, and reading the capacity value C at the moment 0 ；
(4) Selecting C 0 Cells with less than 2% difference;
(5) Taking 1 battery, dismantling, taking out the filler in the central hole, naturally airing for 5min, putting the filler in a vacuum oven at 60 ℃, and baking for 2h;
(6) Taking out the filler, grinding and crushing the filler, and then carrying out digestion test ICP to obtain the content of Li element;
(7) At least 1 additional cell was tested for 100 weeks according to the following procedure:
(7.1) charging the battery to 4.2V under the condition of 0.5C at constant current, charging to 0.05C at constant voltage, stopping, and standing for 5min;
(7.2) discharging the battery to 2.5V under the condition of 0.5C, and standing for 5min;
and (7.3) repeating the step (7.1) and the step (7.2) 100 times, and obtaining a cycle retention rate according to the discharge capacity ratio of the 100 th time to the 1 st time, wherein the difference value between the cycle retention rate and 100% is the cycle attenuation rate.
4. Solid mass ratio test of filler in central hole
Taking at least 3 cylindrical batteries, standing for 1h at normal temperature, then disassembling the batteries, taking out all substances in the central hole, and weighing mass m1; after that, the mixture is baked in a vacuum oven at 100 ℃ for 24 hours, and then the mass m is weighed 2 Obtaining the solid mass ratio m of the filler 2 /ml。
The detection results are as follows:
1. whether or not the central hole is filled with a substance
TABLE 2
As shown in table 2, the center hole filling can improve cycle performance, reduce center hole collapse, improve heat storage, and reduce heat storage gas-generating cover-up by comparison of example 1 and comparative example 1.
2. Lithium salt
TABLE 3 Table 3
As shown in table 3, by comparing examples 1 to 5, it is known that the cycle performance can be improved by adding lithium salt, and the variation trend during the cycle of different types of lithium salt is different, and some lithium salt can be decomposed, and the active lithium loss of the system is supplemented, thereby improving the cycle performance; as is clear from comparing example 1 with example 4, the experiment of 100 weeks shows the relationship between the decomposition efficiency of lithium salt and the cycle, i.e. the higher the decomposition efficiency, the more active lithium is generated by decomposition during the cycle, and part of the lithium is supplemented into the battery cell, so as to improve the cycle performance; as is clear from the comparison between example 1 and comparative example 2, the group to which no lithium salt was added was not affected in terms of structural support and thermal properties, but the cycle retention rate was severely affected, the more salt decomposed, the more the generated channels could adsorb some gases generated in the subsequent thermal storage, thereby lowering the rate of opening the cover and improving the storage performance.
3. Different fillings
TABLE 4 Table 4
As shown in table 4, it is apparent from the comparison of examples 1 and examples 7 to 10 that the filler prepared by adding different polymer materials can improve the storage performance, and the carbon material added inside can additionally adsorb gas, thereby reducing the storage gas production, improving the storage passing rate and reducing the cover opening rate as well as the storage performance.
4. The ratio y of the volume of the filler to the volume of the central hole
TABLE 5
As shown in table 5, it is understood from comparing examples 1, 13 and 14 that if the filling ratio is low, the mechanical supporting effect is deteriorated and the ability to adsorb gas and the ability to replenish lithium are also correspondingly lowered; on the other hand, as is clear from comparative examples 1 and 3, if the filling ratio is too low, there is little supporting effect, and the effects of the center Kong Tanta after circulation, the 1-hour passage rate at 130℃and the 1-hour uncovering rate at 130℃cannot be improved; as is clear from comparison of examples 1, 11 and 12, if the filling ratio is too high, the center hole stress is excessively large, and the cycle performance is also deteriorated.
5. Lithium content a in the filler
TABLE 6
As shown in table 6, it is clear from comparison of examples 1, 15 and 17 that the addition amount of lithium salt is too small to improve the cycle performance; as is apparent from the comparison of example 1, example 16 and comparative example 4, if the amount of lithium salt added is too large, the stability of the center-fill is affected, and the gas generation is largely decomposed, thereby deteriorating the storage performance and the storage cover rate.
6. Filling mode
TABLE 7
Note that: firstly, preparing a cylindrical solid needle with the diameter of 0.1-6mm, and then putting the cylindrical solid needle into a central hole; the method B is that the lithium salt and the filling material are pre-heated and then extruded to be directly filled into the central hole; y is the ratio of the volume of the filler to the volume of the central bore.
As shown in table 7, comparing example 1 with examples 19 and 20, it is known that the cylindrical solid needle inserted in advance affects the effect of the subsequent extrusion, causing local unevenness, thereby affecting the cycle performance; as is clear from comparing example 1 with example 18, the placement of the cylindrical solid needle alone affects the center supporting effect, thereby reducing the mechanical stability improving effect.
7. The mass of the filling occupies the range of mass (specific gravity) of the substance in the central hole
TABLE 8
As shown in table 8, comparing example 1 and example 22, it is known that the mechanical strength can be increased by adding a proper amount of lithium salt, and meanwhile, some lithium can be supplemented to improve the cycle performance; as is clear from comparison between example 1 and example 21, the polymer material can provide crosslinkability and can be integrally molded to increase mechanical strength; as can be seen from comparing example 1 with example 21, the carbon material can adsorb gas, and reduce the gas production in storage. Therefore, when the addition ratio of the substances is greatly changed, the corresponding functions are also changed, thereby affecting the overall effect. As is clear from comparison between example 1 and example 23, when the molecular weight is too low, the mechanical property improving effect is greatly reduced because the filler is not crosslinked and molded.
8. Cylinders of different sizes
TABLE 9
As shown in table 9, it is understood from comparing example 1 with examples 24 to 26 that a cylindrical battery designed with high energy density according to the present invention is applicable to various kinds of batteries with different structures.
9. Cylinder of different chemical systems
Table 10
TABLE 11
As shown in tables 10 and 11, it is understood from a comparison of example 1 and examples 27 to 29 that a high energy density cylindrical battery designed according to the present invention is suitable for use in batteries of various chemical systems designed differently.
Table 12
As shown in Table 12, it is apparent from the comparison of examples 1 and 30 to 31 that the cylindrical battery having a high energy density according to the present invention has a solid portion of the filler in the center hole of 0.6 to 0.99, and is excellent in the cycle performance, the rate of Kong Tanta at the center after the cycle, the rate of 1 hour passage at 140℃and the rate of 1 hour uncovering at 140℃because the filler, electrolyte, gas and the like are contained in the center material of the cylindrical battery, and the function of the filler is impaired when the ratio of other materials is too high, thereby affecting the actual improvement.
In summary, according to the cylindrical battery winding core and the cylindrical battery with the high-energy density design, the lithium salt, the carbon material and the high-molecular material are mixed, so that the mechanical strength of the winding core is further improved, the supporting effect is enhanced, the mechanical stability is improved, and the lithium salt can be used for supplementing lithium after the active lithium in the battery circulation process is consumed, so that the circulation performance is improved. When the lithium salt is consumed, the remaining porous structure can store gas, so that the quantity of the heat storage gas is further reduced, and the heat storage safety performance, particularly the heat storage performance after circulation, is improved.
It should be noted that the above embodiments are only for illustrating the technical solution of the present invention and not for limiting the same, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present invention may be modified or substituted without departing from the spirit and scope of the technical solution of the present invention, which is intended to be covered in the scope of the claims of the present invention.
Claims (10)
1. A cylindrical battery core of high energy density design, comprising: the lithium ion battery comprises a positive plate, a negative plate and a diaphragm, wherein the positive plate is separated from the negative plate through the diaphragm, the positive plate, the negative plate and the diaphragm are wound to form a hollow cylinder structure, a central hole is formed in the hollow cylinder structure, and a filler is filled in the central hole and is a mixture of lithium salt, carbon material and high polymer material.
2. A high energy density engineered cylindrical battery core as in claim 1, wherein: the lithium salt is selected from lithium carbonate, lithium fluoride, lithium oxalate and Li 2 NiO 2 Or any one or more of lithium squarates.
3. A high energy density engineered cylindrical battery core as in claim 1, wherein: the carbon material is selected from any one or two of porous carbon or carbon powder.
4. A high energy density engineered cylindrical battery core as in claim 1, wherein: the polymer material is selected from one or more of PP, PET, PI or PFA.
5. A high energy density engineered cylindrical battery core as in claim 1, wherein: and if the ratio of the volume of the filler to the volume of the central hole is y, y is more than or equal to 0.4 and less than or equal to 0.8.
6. A high energy density engineered cylindrical battery core as in claim 1, wherein: and if the mass percentage of lithium in the filler is a, the mass percentage of the lithium in the filler is more than or equal to 0.1% and less than or equal to 5%.
7. A high energy density engineered cylindrical battery core as in claim 1, wherein: the preparation method of the filler comprises the following steps:
step one: fully stirring the lithium salt, the carbon material and the polymer material in a magnetic stirrer at a rotating speed of 200r/min for 6 hours, then placing the mixture into a box-type furnace with the temperature of 120-400 ℃ and placing the mixture in N 2 Maintaining for 10-30min under atmosphere to obtain mixture;
step two: the mixture was charged into a twin screw extruder, extruded into the central bore at a rate of 5g/min using a 2.5mm extrusion head, and left at room temperature for 3 hours to form a charge.
8. A high energy density engineered cylindrical battery core as in claim 7, wherein: the mass ratio of the solid part of the filler to the mass of the substance in the central hole is 0.6-0.99.
9. A high energy density engineered cylindrical battery core as in claim 1, wherein: when charging and discharging cycles are carried out by 0.5C charging and 0.5C discharging, the relationship between the mass of the filler and the charging and discharging cycles is as follows: and (3) assuming that the mass percentage of lithium in the filler after 100 weeks of circulation is b, the mass percentage of lithium in the filler before circulation is a, and the capacity fading percentage after 100 weeks of circulation is x, a/b is less than or equal to 150x, wherein when x is less than 1%, the value of x is 1%.
10. A cylindrical battery having a high energy density engineered cylindrical battery cell as in any of claims 1-9, wherein: the diameter of the cylindrical battery is 20-50mm, and the height of the cylindrical battery is 60-150mm.
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