CN114551960B - Lithium ion battery lamination unit, preparation method thereof and lithium ion battery comprising lithium ion battery lamination unit - Google Patents
Lithium ion battery lamination unit, preparation method thereof and lithium ion battery comprising lithium ion battery lamination unit Download PDFInfo
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- CN114551960B CN114551960B CN202110837146.1A CN202110837146A CN114551960B CN 114551960 B CN114551960 B CN 114551960B CN 202110837146 A CN202110837146 A CN 202110837146A CN 114551960 B CN114551960 B CN 114551960B
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- lithium ion
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- 238000003475 lamination Methods 0.000 title claims abstract description 56
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CVJYOKLQNGVTIS-UHFFFAOYSA-K aluminum;lithium;titanium(4+);phosphate Chemical compound [Li+].[Al+3].[Ti+4].[O-]P([O-])([O-])=O CVJYOKLQNGVTIS-UHFFFAOYSA-K 0.000 claims abstract description 36
- 238000000576 coating method Methods 0.000 claims abstract description 34
- 229910021525 ceramic electrolyte Inorganic materials 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 30
- 239000011248 coating agent Substances 0.000 claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 25
- 238000001354 calcination Methods 0.000 claims description 24
- 229910000664 lithium aluminum titanium phosphates (LATP) Inorganic materials 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 239000011343 solid material Substances 0.000 claims description 15
- AIFLGMNWQFPTAJ-UHFFFAOYSA-J 2-hydroxypropanoate;titanium(4+) Chemical compound [Ti+4].CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O.CC(O)C([O-])=O AIFLGMNWQFPTAJ-UHFFFAOYSA-J 0.000 claims description 14
- 229910052744 lithium Inorganic materials 0.000 claims description 13
- 239000002033 PVDF binder Substances 0.000 claims description 12
- 239000011812 mixed powder Substances 0.000 claims description 12
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 12
- 229910004283 SiO 4 Inorganic materials 0.000 claims description 11
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 10
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 10
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 10
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 10
- 238000007731 hot pressing Methods 0.000 claims description 10
- -1 polypropylene Polymers 0.000 claims description 10
- 239000004698 Polyethylene Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229920000573 polyethylene Polymers 0.000 claims description 8
- 238000004090 dissolution Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 6
- 238000013329 compounding Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 abstract description 10
- 230000000052 comparative effect Effects 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 239000006255 coating slurry Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910013553 LiNO Inorganic materials 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 210000004027 cell Anatomy 0.000 description 4
- 238000005524 ceramic coating Methods 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000017525 heat dissipation Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/04—Construction or manufacture in general
- H01M10/0459—Cells or batteries with folded separator between plate-like electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0561—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of inorganic materials only
- H01M10/0562—Solid materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
- H01M10/0583—Construction or manufacture of accumulators with folded construction elements except wound ones, i.e. folded positive or negative electrodes or separators, e.g. with "Z"-shaped electrodes or separators
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a lithium ion battery lamination unit, a preparation method thereof and a lithium ion battery comprising the same, wherein the lamination unit comprises a plurality of positive plates and negative plates which are alternately arranged, and a Z-shaped folded continuous diaphragm for separating the positive plates and the negative plates; the two sides of the continuous diaphragm are coated with electrolyte coating, and the electrolyte coating comprises 80-100 parts by weight of titanium aluminum lithium phosphate ceramic electrolyte and 60-80 parts by weight of binder. The preparation method comprises the following steps: respectively bonding the positive plate and the negative plate at the corresponding positions on two sides of the continuous diaphragm after the electrolyte coating is coated, so as to obtain a plurality of groups of pole plate pairs with equal spacing; and folding the continuous diaphragm according to a Z shape from between each pole piece pair to obtain the lamination unit. According to the invention, the electrolyte coating containing the titanium aluminum lithium phosphate ceramic is coated on both sides of the continuous diaphragm, so that the thermal shrinkage of the diaphragm can be reduced, and the capacity performance of the battery can be improved; the lamination unit has high production efficiency and high lamination quality.
Description
Technical Field
The invention relates to the field of lithium ion batteries, in particular to a lithium ion battery lamination unit, a preparation method thereof and a lithium ion battery comprising the lithium ion battery lamination unit.
Background
The preparation of the battery core is an important procedure in the manufacturing process of the lithium ion battery, and the traditional battery core preparation of the lithium ion battery with small capacity mainly adopts a winding mode, namely, a long sheet positive electrode and a long sheet negative electrode are wound together with an inserted diaphragm; the mode has higher efficiency, and the produced batteries have better consistency, but the produced batteries have larger impedance and poor heat dissipation performance of the battery core, are not suitable for being used as power batteries, and are generally used in the manufacture of small-capacity batteries used by electronic equipment.
The high-capacity lithium ion power battery is generally manufactured by adopting lamination, namely, pole rolls of the prepared positive pole piece and the prepared negative pole piece are cut to prepare pole pieces with required sizes, and then the cut positive pole piece, the cut negative pole piece and the cut diaphragm are stacked in a certain order to prepare the battery cell. For example, a "a lithium ion battery zigzag lamination device and process thereof" disclosed in chinese patent literature, its publication number CN109244554B, the lithium ion battery zigzag lamination process includes the following steps: (1) Firstly, die cutting or cutting the positive electrode roll and the negative electrode roll, and then respectively adhering a die-cut or cut negative electrode piece and a cut positive electrode piece on the upper surface and the lower surface of the diaphragm, wherein the positive electrode piece and the negative electrode piece are distributed in a staggered way; (2) Then carrying out hot-pressing compounding on the diaphragm, each negative plate and each positive plate; (3) finally performing Z-shaped folding and cutting the diaphragm. The battery prepared by the method has small impedance and good heat dissipation performance, and is suitable for preparing a large-capacity lithium ion battery. However, the preparation efficiency of the lamination type battery is lower than that of the winding type battery, when the battery core is manufactured, the positions of the pole pieces and the diaphragms need to be aligned strictly, dislocation is avoided, the capacity of part of the pole pieces cannot be fully utilized, or the contact of the positive pole pieces and the negative pole pieces causes short circuit, and then the safety problem is caused. In order to ensure that dislocation occurs between the pole piece and the diaphragm, a relatively complex tool is adopted to control the positions and the movements of the pole piece and the diaphragm under the normal condition, and even manual operation is added to improve the alignment precision of the battery cell. Therefore, the production efficiency of the battery is greatly reduced, higher alignment precision is difficult to achieve, the dislocation phenomenon of the pole piece still occurs in the manufactured lithium ion battery, the capacity of the battery is reduced, and even safety accidents are caused.
In addition, the separator used in the lithium ion battery at present is mainly formed by coating a layer of uniform ceramic powder on at least one surface of a polyolefin separator, and the excellent heat resistance of a ceramic material is utilized to reduce the thermal shrinkage of the separator, so that the safety of the battery is ensured. However, the traditional separator coated with the ceramic layer is unfavorable for the capacity exertion under the condition of high-rate charge and discharge of the lithium ion battery because the conductivity of lithium ions in the ceramic layer is low.
Disclosure of Invention
The invention aims to solve the problems that in the prior art, high alignment precision is difficult to achieve in a lamination process, so that the production efficiency of a battery is low and the capacity performance of the battery is poor.
The second invention aims to solve the problems that in the prior art, the conducting capacity of lithium ions in a ceramic layer is low in the membrane coated with the ceramic layer, and the capacity of a lithium ion battery is not conveniently exerted under the condition of high-rate charge and discharge, and provides a lithium ion battery lamination unit, a preparation method thereof and a lithium ion battery comprising the same.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a lithium ion battery lamination unit comprises a plurality of positive plates and negative plates which are alternately arranged, and a continuous diaphragm which is used for separating the positive plates and the negative plates and is folded in a Z shape; both sides of the lamination unit are negative plates; electrolyte coating layers are coated on two sides of the continuous diaphragm, and the electrolyte coating layers comprise 80-100 parts by weight of lithium aluminum titanium phosphate ceramic electrolyte and 60-80 parts by weight of binder.
The invention also provides a preparation method of the lamination unit, which comprises the following steps:
(1) Respectively coating electrolyte coatings on two sides of the continuous diaphragm;
(2) Respectively placing the positive plate and the negative plate at the corresponding positions of the two sides of the coated continuous diaphragm, and bonding the positive plate and the negative plate on the two sides of the continuous diaphragm through hot-pressing compounding to obtain a group of plate pairs; bonding the rest positive plates and the rest negative plates on two sides of the continuous diaphragm by the same method to form a plurality of groups of pole plate pairs, so that the distances between the pole plate pairs are equal;
(3) And folding the continuous diaphragm according to a Z shape from between each pole piece pair to obtain the lamination unit.
According to the invention, the positive and negative pole pieces are respectively bonded at the corresponding positions on the two sides of the continuous diaphragm during preparation of the lamination unit, so that a plurality of groups of pole piece pairs are formed, the relative positions between two adjacent positive and negative pole pieces are easy to control, and the positive and negative pole pieces are bonded on the continuous diaphragm, so that the positions of the positive and negative pole pieces can be prevented from moving in the subsequent lamination process, and the lamination precision is improved; and then the continuous diaphragm is folded according to a Z shape between each pair of pole pieces to obtain a lamination unit, the distance between each pair of pole pieces can be adjusted and controlled according to lamination requirements, the production efficiency of the lamination unit is high, the alignment degree between electrodes is well controlled, the lamination quality is high, and adverse conditions such as diaphragm folding and the like are not easy to occur.
In addition, the electrolyte coating containing the titanium aluminum lithium phosphate ceramic is coated on the two sides of the continuous diaphragm, and the titanium aluminum lithium phosphate ceramic is a solid electrolyte, so that the conductivity of lithium ions in the coating can be effectively improved, and the capacity performance of the battery can be improved; meanwhile, the titanium aluminum lithium phosphate ceramic has excellent heat resistance, and can reduce the thermal shrinkage of the diaphragm, so that the contact short circuit of the anode and the cathode caused by the thermal shrinkage of the diaphragm is avoided, even explosion is avoided, and the safety of the battery is ensured.
Preferably, the binder comprises PVDF and carboxymethyl cellulose in a mass ratio of 5-7:1. PVDF and carboxymethyl cellulose are adopted as binders in the electrolyte coating, and the PVDF can be changed into a molten state in the hot pressing process, so that positive and negative plates can be effectively bonded on the surface of the diaphragm, and the lamination precision is improved.
Preferably, the preparation method of the lithium aluminum titanium phosphate ceramic electrolyte comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding the mixture into a solvent for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 70-80 ℃ for 10-20 hours to obtain viscous liquid; calcining the viscous liquid at 200-250 ℃ for 10-30 min, and then calcining at 300-350 ℃ for 2-3 h to obtain a solid material; mixing the solid material with Li 4 SiO 4 Mixing and ball milling to obtain mixed powder, calcining the mixed powder at 600-750 ℃ for 1-3 h to obtainTo the lithium aluminum titanium phosphate ceramic electrolyte.
The invention dopes CsClO in the prepared lithium aluminum titanium phosphate ceramic electrolyte 4 The reduction potential of the Cs element is lower than that of the Li element, and the electrostatic shielding effect is achieved, so that the lithium element is forced to be deposited in the area around the Cs element, the uniformity of lithium deposition is further improved, continuous growth of lithium dendrites at a certain fixed position is avoided, and the cycle performance of the battery is reduced. And, li is added in the calcining process 4 SiO 4 As a sintering aid, the sintering temperature (from the conventional temperature of more than 1000 ℃ to 600-750 ℃) can be reduced, the loss of lithium element in the high-temperature sintering process is reduced, and meanwhile, the ion conductivity of the titanium aluminum lithium phosphate ceramic electrolyte can be improved, and the main reason is Si 4+ Ion occupies Al 3+ Bit and Li + The redundant lithium ions occupy the gap positions, so that the lithium ion gaps are increased, the lithium ion conductivity is increased, and the conductivity of lithium ions in the coating is further improved.
Preferably, in preparing a viscous liquid, liNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The adding amount of (2) is 1.2-1.4:0.2-0.4:1.6-1.8:3 according to the mol ratio of Li, al, ti, P, and the CsClO is prepared by the following steps 4 The addition amount of the liquid is 1 to 3 percent of the total mass of the viscous liquid; the mole ratio of the added citric acid to the metal elements in the solution is 1:1-1.5. The optimal doping amount of Cs is 1-3%, the electrostatic shielding effect is not obvious when the doping amount is too low, and the Cs are unevenly dispersed when the doping amount is too high, so that the electrostatic shielding effect is weakened.
Preferably, the solid material and Li in the powder are mixed 4 SiO 4 The mass ratio of (2) is 25-30:1.
Preferably, the continuous separator is a polypropylene or polyethylene separator having a thickness of 6 to 25 μm.
Preferably, the electrolyte coating has a thickness of 1 to 5 μm.
The invention also provides an application of the lamination unit in a lithium ion battery, wherein the lithium ion battery can be a secondary battery, a module containing a plurality of secondary batteries or a battery pack containing a plurality of battery modules.
Therefore, the invention has the following beneficial effects:
(1) The production efficiency of the lamination unit is high, the alignment degree between the electrodes is well controlled, the lamination quality is high, and the adverse conditions such as diaphragm folding and the like are not easy to occur;
(2) Electrolyte coatings containing lithium aluminum titanium phosphate ceramics are coated on two sides of the continuous diaphragm, so that the thermal shrinkage of the diaphragm can be reduced, the safety of the battery is improved, and the capacity performance of the battery is improved;
(3) CsClO doping in lithium aluminum titanium phosphate ceramic electrolyte 4 The reduction potential of the Cs element is lower than that of the Li element, and the lithium element is forced to be deposited in the surrounding area of the Cs element, so that the uniformity of lithium deposition is further improved, and continuous growth of lithium dendrites at a certain fixed position is avoided, so that the cycle performance of the battery is improved.
Drawings
Fig. 1 is a schematic view of a process for manufacturing a lamination unit of the present invention.
In the figure: 1 positive plate, 2 negative plate, 3 continuous diaphragm, 100 hot press roller, 200 stacking mechanism, 300 picture peg device.
Detailed Description
The invention is further described below with reference to the drawings and detailed description.
In the present invention, all the equipment and raw materials are commercially available or commonly used in the industry, and the methods in the following examples are conventional in the art unless otherwise specified.
Example 1:
a lithium ion battery lamination unit comprises 20 positive plates and 21 negative plates which are alternately arranged, and a continuous diaphragm which is used for separating the positive plates from the negative plates and is folded in a Z shape; both sides of the lamination unit are negative plates. The continuous diaphragm adopts a polyethylene diaphragm with the thickness of 20 mu m, two sides of the polyethylene diaphragm are respectively coated with electrolyte coatings with the thickness of 3 mu m, and the electrolyte coatings comprise 90 parts of lithium aluminum titanium phosphate ceramic electrolyte, 60 parts of PVDF and 10 parts of carboxymethyl cellulose in parts by weight.
The preparation method of the lithium aluminum titanium phosphate ceramic electrolyte comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding deionized water for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 75 ℃ for 18 hours to obtain viscous liquid; wherein LiNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of (C) is 1.3:0.3:1.7:3, and CsClO is according to the mol ratio of Li, al, ti, P 4 The addition amount of (2) is 2% of the total mass of the viscous liquid; the molar ratio of the added citric acid to the metal elements in the solution is 1:1.2; calcining the viscous liquid at 220 ℃ for 20min, and then calcining at 320 ℃ for 2.5h to obtain a solid material; combining solid material with Li 4 SiO 4 Mixing and ball milling according to the mass ratio of 28:1 to obtain mixed powder, and calcining the mixed powder at 700 ℃ for 2 hours to obtain the titanium aluminum lithium phosphate ceramic electrolyte.
The preparation method of the lamination unit comprises the following steps:
(1) Electrolyte coating layers are respectively coated on two sides of the continuous diaphragm: adding 90 parts of lithium aluminum titanium phosphate ceramic electrolyte, 60 parts of PVDF and 10 parts of carboxymethyl cellulose into 100 parts of deionized water, uniformly stirring to obtain coating slurry, coating the coating slurry on two sides of a continuous diaphragm, and drying to obtain an electrolyte coating;
(2) As shown in fig. 1, a coated continuous diaphragm 3 is placed on a conveying device, then a positive plate 1 and a negative plate 2 are respectively placed at corresponding positions on the upper side and the lower side of the continuous diaphragm, after hot-pressing and compounding by a hot-pressing roller 100, an adhesive PVDF in an electrolyte coating on the surface of the continuous diaphragm can become molten, and the positive plate and the negative plate are adhered on the two sides of the continuous diaphragm, so that a group of plate pairs are obtained; the other positive plates and the negative plates are bonded on two sides of the continuous diaphragm in the same method to form a plurality of groups of pole plate pairs, so that the distances between the pole plate pairs are equal, and the last negative plate is independently bonded on the lower side of the continuous diaphragm;
(3) The lamination unit is obtained by conveying each pair of pole pieces on the continuous diaphragm to the stacking mechanism 200 by a conveying device, and then folding the continuous diaphragm in a Z-shaped manner from between each pair of pole pieces by a plugboard device 300.
Example 2:
a lithium ion battery lamination unit comprises 20 positive plates and 21 negative plates which are alternately arranged, and a continuous diaphragm which is used for separating the positive plates from the negative plates and is folded in a Z shape; both sides of the lamination unit are negative plates. The continuous diaphragm adopts a polyethylene diaphragm with the thickness of 6 mu m, two sides of the polyethylene diaphragm are respectively coated with electrolyte coatings with the thickness of 5 mu m, and the electrolyte coatings comprise 80 parts of lithium aluminum titanium phosphate ceramic electrolyte, 50 parts of PVDF and 10 parts of carboxymethyl cellulose in parts by weight.
The preparation method of the lithium aluminum titanium phosphate ceramic electrolyte comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding deionized water for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 70 ℃ for 20 hours to obtain viscous liquid; wherein LiNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of (C) is 1.4:0.4:1.6:3, and CsClO is according to the mol ratio of Li, al, ti, P 4 The addition amount of (2) is 1% of the total mass of the viscous liquid; the molar ratio of the added citric acid to the metal elements in the solution is 1:1; calcining the viscous liquid at 200 ℃ for 30min, and then calcining at 350 ℃ for 2h to obtain a solid material; combining solid material with Li 4 SiO 4 Mixing and ball milling according to the mass ratio of 25:1 to obtain mixed powder, and calcining the mixed powder at 600 ℃ for 3 hours to obtain the titanium aluminum lithium phosphate ceramic electrolyte.
The preparation method of the lamination unit comprises the following steps:
(1) Electrolyte coating layers are respectively coated on two sides of the continuous diaphragm: adding 80 parts of lithium aluminum titanium phosphate ceramic electrolyte, 50 parts of PVDF and 10 parts of carboxymethyl cellulose into 100 parts of deionized water, uniformly stirring to obtain coating slurry, coating the coating slurry on two sides of a continuous diaphragm, and drying to obtain an electrolyte coating;
(2) Placing the coated continuous diaphragm on a conveying device, respectively placing the positive plate and the negative plate at corresponding positions on the upper side and the lower side of the continuous diaphragm, and bonding the positive plate and the negative plate on the two sides of the continuous diaphragm after hot-pressing and compounding by a hot-pressing roller to obtain a group of plate pairs; the other positive plates and the negative plates are bonded on two sides of the continuous diaphragm in the same method to form a plurality of groups of pole plate pairs, so that the distances between the pole plate pairs are equal, and the last negative plate is independently bonded on the lower side of the continuous diaphragm;
(3) And conveying each pole piece pair on the continuous diaphragm to a stacking mechanism through a conveying device, and then folding the continuous diaphragm between each pole piece pair according to a Z shape through a plugboard device to obtain the lamination unit.
Example 3:
a lithium ion battery lamination unit comprises 20 positive plates and 21 negative plates which are alternately arranged, and a continuous diaphragm which is used for separating the positive plates from the negative plates and is folded in a Z shape; both sides of the lamination unit are negative plates. The continuous diaphragm adopts a polyethylene diaphragm with the thickness of 25 mu m, two sides of the polyethylene diaphragm are respectively coated with an electrolyte coating with the thickness of 1 mu m, and the electrolyte coating comprises 100 parts by weight of lithium aluminum titanium phosphate ceramic electrolyte, 70 parts by weight of PVDF and 10 parts by weight of carboxymethyl cellulose.
The preparation method of the lithium aluminum titanium phosphate ceramic electrolyte comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding deionized water for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 80 ℃ for 10 hours to obtain viscous liquid; wherein LiNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of (C) is 1.2:0.2:1.8:3, and CsClO is according to the mol ratio of Li, al, ti, P 4 The addition amount of (2) is 3% of the total mass of the viscous liquid; the molar ratio of the added citric acid to the metal elements in the solution is 1:1.5; calcining the viscous liquid at 250 ℃ for 10min, and then calcining at 300 ℃ for 3h to obtain a solid material; by applying solid materialAnd Li (lithium) 4 SiO 4 Mixing and ball milling according to the mass ratio of 30:1 to obtain mixed powder, and calcining the mixed powder at 750 ℃ for 1h to obtain the titanium aluminum lithium phosphate ceramic electrolyte.
The preparation method of the lamination unit comprises the following steps:
(1) Electrolyte coating layers are respectively coated on two sides of the continuous diaphragm: adding 100 parts of lithium aluminum titanium phosphate ceramic electrolyte, 70 parts of PVDF and 10 parts of carboxymethyl cellulose into 120 parts of deionized water, uniformly stirring to obtain coating slurry, coating the coating slurry on two sides of a continuous diaphragm, and drying to obtain an electrolyte coating;
(2) Placing the coated continuous diaphragm on a conveying device, respectively placing the positive plate and the negative plate at corresponding positions on the upper side and the lower side of the continuous diaphragm, and bonding the positive plate and the negative plate on the two sides of the continuous diaphragm after hot-pressing and compounding by a hot-pressing roller to obtain a group of plate pairs; the other positive plates and the negative plates are bonded on two sides of the continuous diaphragm in the same method to form a plurality of groups of pole plate pairs, so that the distances between the pole plate pairs are equal, and the last negative plate is independently bonded on the lower side of the continuous diaphragm;
(3) And conveying each pole piece pair on the continuous diaphragm to a stacking mechanism through a conveying device, and then folding the continuous diaphragm between each pole piece pair according to a Z shape through a plugboard device to obtain the lamination unit.
Comparative example 1 (ceramic coating instead of electrolyte coating):
the continuous separator of comparative example 1 was coated on both sides with a ceramic coating comprising, in parts by weight, 90 parts of alumina, 60 parts of PVDF and 10 parts of carboxymethyl cellulose. The remainder was the same as in example 1.
Comparative example 2 (titanium aluminum phosphate lithium ceramic electrolyte undoped CsClO 4 Modified):
the preparation method of the lithium aluminum titanium phosphate ceramic electrolyte in comparative example 2 comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O and NH 4 H 2 PO 4 Adding deionized water for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 75 ℃ for 18 hours to obtain viscous liquid; which is a kind ofIn LiNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of (2) is 1.3:0.3:1.7:3 according to the mol ratio of Li, al, ti, P; the molar ratio of the added citric acid to the metal elements in the solution is 1:1.2; calcining the viscous liquid at 220 ℃ for 20min, and then calcining at 320 ℃ for 2.5h to obtain a solid material; combining solid material with Li 4 SiO 4 Mixing and ball milling according to the mass ratio of 28:1 to obtain mixed powder, and calcining the mixed powder at 700 ℃ for 2 hours to obtain the titanium aluminum lithium phosphate ceramic electrolyte. The remainder was the same as in example 1.
Comparative example 3 (lithium aluminum titanium phosphate ceramic electrolyte calcination without Li addition 4 SiO 4 )：
The preparation method of the lithium aluminum titanium phosphate ceramic electrolyte in the comparative example 3 comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 ·9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding deionized water for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 75 ℃ for 18 hours to obtain viscous liquid; wherein LiNO 3 、Al(NO 3 ) 3 ·9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of (C) is 1.3:0.3:1.7:3, and CsClO is according to the mol ratio of Li, al, ti, P 4 The addition amount of (2) is 2% of the total mass of the viscous liquid; the molar ratio of the added citric acid to the metal elements in the solution is 1:1.2; calcining the viscous liquid at 220 ℃ for 20min, and then calcining at 320 ℃ for 2.5h to obtain a solid material; calcining the solid material at 700 ℃ for 2 hours to obtain the lithium aluminum titanium phosphate ceramic electrolyte. The remainder was the same as in example 1.
After the lamination units in the above examples and comparative examples were assembled into bare cells, soft package cells were fabricated through welding, packaging, liquid injection and formation processes, and performance thereof was tested. The invention selects the discharge internal resistance, the low-temperature discharge capacity, the multiplying power discharge capacity and the low-temperature circulation which are relatively sufficient in the dynamic performance characterization of the lithium ion battery as evaluation items (specific test conditions are that the impedance of 30s pulse discharge of the battery in a state of normal temperature of 50% SOC is selected as the evaluation condition of the discharge internal resistance, the capacity test is carried out at the low temperature of-10 ℃, the charging multiplying power is C/5, the discharging multiplying power is C/3, the multiplying power test is carried out at the normal temperature, the charging adopts C/3, the discharging adopts 3C, the circulation performance is carried out at the low temperature of-10 ℃, the charging multiplying power is C/5, the discharging multiplying power is C/3, and the test cut-off condition is that the capacity retention rate is attenuated to 80%), and the results are shown in a table 1.
Table 1: and (5) testing the performance of the lithium ion battery.
| Test item | Example 1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Internal resistance of discharge/mΩ | 1.45 | 1.53 | 1.55 | 1.66 | 1.71 | 1.74 |
| Discharge capacity/Ah | 71.5 | 67.7 | 64.0 | 51.3 | 54.9 | 57.3 |
| Rate capability/Ah | 59.2 | 55.1 | 53.8 | 42.4 | 46.8 | 49.5 |
| Cycle performance/loop | 800 | 762 | 745 | 480 | 535 | 628 |
As can be seen from table 1, the lithium ion batteries prepared by using the lamination unit in examples 1 to 3 have good capacity, multiplying power and cycle performance, and the proportion in example 1 is the optimal choice; the continuous diaphragm in comparative example 1 is coated with a traditional ceramic coating, but not the electrolyte coating in the invention, the impedance, capacity performance and multiplying power performance of the battery are all obviously reduced, which shows that the lithium aluminum titanium phosphate ceramic electrolyte is loaded on the diaphragm, so that the conductivity of lithium ions in the coating can be effectively improved; comparative example 2 preparation of lithium aluminum titanium phosphate ceramic electrolyte without CsClO doping 4 The lithium dendrite cannot be restrained from growing after modification, and various electrochemical performances of the battery are also reduced; comparative example 3 in which Li was not added during calcination of the lithium aluminum titanium phosphate ceramic electrolyte 4 SiO 4 As an aidThe burn agent, the lithium ion transmission performance of the material is reduced, and the performance of the battery is reduced.
Claims (8)
1. The lithium ion battery lamination unit is characterized by comprising a plurality of positive plates and negative plates which are alternately arranged, and a continuous diaphragm which is used for separating the positive plates and the negative plates and is folded in a Z shape; both sides of the lamination unit are negative plates; electrolyte coatings are coated on two sides of the continuous diaphragm, and the electrolyte coatings comprise 80-100 parts by weight of lithium aluminum titanium phosphate ceramic electrolyte and 60-80 parts by weight of binder;
the preparation method of the lithium aluminum titanium phosphate ceramic electrolyte comprises the following steps: liNO is to be carried out 3 、Al(NO 3 ) 3 •9H 2 O、NH 4 H 2 PO 4 And CsClO 4 Adding the mixture into a solvent for dissolution, then adding citric acid, uniformly stirring, then adding titanium lactate, and stirring at 70-80 ℃ for 10-20 hours to obtain a viscous liquid; calcining the viscous liquid at 200-250 ℃ for 10-30 min, and then calcining at 300-350 ℃ for 2-3 h to obtain a solid material; mixing the solid material with Li 4 SiO 4 Mixing and ball milling to obtain mixed powder, and calcining the mixed powder at 600-750 ℃ for 1-3 hours to obtain the titanium aluminum lithium phosphate ceramic electrolyte.
2. The lithium ion battery lamination unit according to claim 1, wherein the binder comprises PVDF and carboxymethyl cellulose in a mass ratio of 5-7:1.
3. The lithium-ion battery lamination unit according to claim 1, wherein when preparing a viscous liquid, liNO 3 、Al(NO 3 ) 3 •9H 2 O, titanium lactate and NH 4 H 2 PO 4 The addition amount of the CsClO is 1.2-1.4:0.2-0.4:1.6-1.8:3 according to the mol ratio of Li, al, ti, P 4 The addition amount of the liquid is 1-3% of the total mass of the viscous liquid; the molar ratio of the added citric acid to the metal elements in the solution is 1:1-1.5.
4. A lithium ion battery laminate unit according to claim 1 or 3, characterized in that the solid material and Li in the powder are mixed 4 SiO 4 The mass ratio of (2) is 25-30:1.
5. The lithium ion battery lamination unit according to claim 1, wherein the continuous diaphragm is a polypropylene or polyethylene diaphragm with a thickness of 6-25 [ mu ] m.
6. The lithium ion battery lamination unit according to claim 1 or 5, wherein the electrolyte coating has a thickness of 1-5 μm.
7. A method of manufacturing a lamination unit as defined in any one of claims 1 to 6, comprising the steps of:
(1) Respectively coating electrolyte coatings on two sides of the continuous diaphragm;
(2) Respectively placing the positive plate and the negative plate at the corresponding positions of the two sides of the coated continuous diaphragm, and bonding the positive plate and the negative plate on the two sides of the continuous diaphragm through hot-pressing compounding to obtain a group of plate pairs; bonding the rest positive plates and the rest negative plates on two sides of the continuous diaphragm by the same method to form a plurality of groups of pole plate pairs, so that the distances between the pole plate pairs are equal;
(3) And folding the continuous diaphragm according to a Z shape from between each pole piece pair to obtain the lamination unit.
8. Use of a lamination unit according to any one of claims 1 to 6 in a lithium ion battery.
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