CN113363419B - Negative pole piece and preparation method and application thereof - Google Patents
Negative pole piece and preparation method and application thereof Download PDFInfo
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- CN113363419B CN113363419B CN202110696472.5A CN202110696472A CN113363419B CN 113363419 B CN113363419 B CN 113363419B CN 202110696472 A CN202110696472 A CN 202110696472A CN 113363419 B CN113363419 B CN 113363419B
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Abstract
The invention provides a negative pole piece and a preparation method and application thereof; the negative pole piece comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through the design of a three-layer structure and the special selection of each layer of structure, when the negative pole piece is applied to the lithium ion battery, a layer of compact passivation film can be formed on the surface of the negative pole piece, so that the lithium dendrite is prevented from piercing a lithium ion battery diaphragm to cause the short circuit of the battery, and the safety performance of the lithium ion battery is improved; the negative pole piece is matched with the preparation method of the lithium ion battery provided by the invention, so that the dissolution of Mn ions in the positive pole material can be inhibited, the using amount of the electrolyte is reduced, the safety performance of the lithium ion battery is further improved, and the preparation method has important research significance.
Description
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a negative pole piece and a preparation method and application thereof.
Background
At present, the lithium ion battery mainly takes liquid electrolyte as a main component, but the liquid battery has the problems of poor safety performance, inflammability, large interface resistance, weak ion transmission capability, poor performance such as poor charge and discharge performance, poor multiplying power cycle performance and the like at normal temperature, and further cannot realize commercial production.
The interface problem which is difficult to solve in the all-solid-state battery is the biggest obstacle for limiting the practical application of the all-solid-state battery, the polymer electrolyte has good flexibility and can ensure better interface contact in the battery, the oxide electrolyte has higher lithium ion conductivity and safety performance, and the combination of the polymer electrolyte and the oxide electrolyte for preparing the battery is hopeful to obtain the all-solid-state battery with electrochemical performance meeting the actual requirement. Currently, a PEO-based polymer electrolyte is mostly used for assembling an all-solid-state battery in research, the PEO-based polymer electrolyte has the advantages of good low-voltage stability, low interface impedance and the like, but is oxidized and decomposed at a voltage of more than 4V, and only a lithium iron phosphate material can be matched with a common positive electrode material, so that the energy density of the battery is limited. Meanwhile, the conductivity of the PEO-based polymer electrolyte is low, and the assembled all-solid-state battery can only operate at high temperature and low rate.
Therefore, research into solid state lithium ion batteries is still ongoing. CN112467117A discloses a graphite composite material coated by lithium aluminum titanium phosphate, a preparation method thereof and a battery cathode. The lithium titanium aluminum phosphate coated graphite composite material comprises: the inner core comprises graphite; the shell layer is coated outside the inner core, and the material of the shell layer comprises titanium aluminum lithium phosphate and carbon; and the passivation layer is coated outside the shell. The titanium aluminum lithium phosphate and the carbon are coated outside the graphite, so that the conductivity can be improved, the titanium aluminum lithium phosphate has higher lithium ion conductivity, the transmission efficiency of lithium ions can be improved, and compared with other materials, the titanium aluminum lithium phosphate has the characteristics of stable structure, strong chemical stability, good cycle performance and the like. The passivation layer has a passivation effect on the lithium titanium aluminum phosphate, reduces the occurrence of side reactions of the lithium titanium aluminum phosphate, and improves the storage performance and the cycle performance of the lithium titanium aluminum phosphate, thereby improving the transmission efficiency, the rate capability and the safety performance of lithium ions of the lithium titanium aluminum phosphate coated graphite composite material. However, the preparation process of the battery is complex, high in cost and long in manufacturing period, and is not beneficial to large-scale and large-scale production and application.
CN111384436A discloses an all-solid-state lithium ion battery prepared by coating solid electrolyte slurry on a composite negative electrode plate and a preparation method thereof, the invention firstly uses aqueous polymer solid electrolyte to prepare the composite negative electrode plate, then coats slurry mixed with oily organic binder and high oxide solid electrolyte content on the composite negative electrode plate, dries and rolls the slurry, and then assembles the battery with a composite positive electrode prepared by high-pressure resistant oily polymer electrolyte. And adding a small amount of organic solvent between the positive electrode and the negative electrode in the battery assembly process to wet an interface, and drying the organic solvent before packaging the battery. The all-solid-state battery assembled by the method has excellent safety performance, high energy density and good cycle performance. CN112670450A discloses a negative electrode plate for a solid-state battery, and a preparation method and use thereof; the negative pole piece comprises a copper foil, a lithium metal layer, a lithium nitride layer and an organic-inorganic composite layer which are sequentially stacked. According to the invention, ultrathin and uniform electroplated lithium metal is used as a base material, surface modification is carried out on the surface of the ultrathin and uniform electroplated lithium metal through nitrogen so that the lithium metal is uniformly deposited, short circuit is prevented, the loss of a lithium source in the circulation process is slowed down, and then an organic-inorganic composite coating is compounded on the surface of the treated lithium metal so that the lithium metal deposited by charging deposition is more uniformly and compactly deposited, the occurrence of short circuit is effectively inhibited, and the interface reaction generated by direct contact of the lithium metal and an electrolyte is inhibited, so that the circulation performance is improved; however, the solid-state batteries prepared by the two methods still have certain potential safety hazards in use.
Therefore, it is a technical problem to be solved urgently in the field to develop a negative electrode plate which can form a dense passivation film on the surface when in use.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a negative pole piece and a preparation method and application thereof, wherein the negative pole piece comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through three-layer structure design and special selection of materials in each layer of structure, when the obtained negative pole piece is applied to the lithium ion battery, a layer of compact passivation film is formed on the surface of the pole piece, the passivation film can avoid safety problems of battery short circuit, explosive combustion and the like caused by the fact that lithium dendrites pierce through a lithium ion battery diaphragm, and further safety performance of the lithium ion battery is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a negative electrode plate, which includes a current collector, an active material layer, and a Ti-containing oxide solid electrolyte layer, which are sequentially disposed.
The schematic cross-sectional structure of the negative electrode plate provided by the invention is shown in fig. 1, wherein 1 represents a current collector, 2 represents an active material layer, and 3 represents a Ti-containing oxide solid electrolyte layer; according to the negative pole piece provided by the invention, through the design of a three-layer structure, and the specific selection of materials in each layer, a compact passivation film can be formed on the surface of the negative pole piece when the negative pole piece is applied to a lithium ion battery, the passivation film can effectively prevent the lithium ion battery short circuit problem caused by the growth of lithium dendrites, and can also reduce the occurrence of side reactions of an oxide solid electrolyte layer material containing Ti, so that the long-term cycle performance, the high-temperature cycle performance and the safety performance of the lithium ion battery can be effectively improved, and the negative pole piece has important research significance.
The Ti-containing oxide material of the Ti-containing oxide solid electrolyte layer in the negative pole piece has high lithium ion conductivity, so that the transmission efficiency of lithium ions can be improved.
Preferably, the thickness of the negative electrode sheet is 80-200 μm, such as 100 μm, 120 μm, 140 μm, 160 μm or 180 μm, and specific values therebetween are not exhaustive for the invention, which is limited to specific values included in the ranges for brevity and conciseness.
Preferably, the current collector comprises a copper foil.
Preferably, the active material layer has a thickness of 70 to 190 μm, for example 80 μm, 90 μm, 100 μm, 120 μm, 140 μm, 160 μm or 180 μm, and specific values therebetween, which are not exhaustive for the invention and are included in the range for brevity. .
Preferably, the material of the active material coating layer includes a combination of a negative electrode active material, a conductive agent, and a binder.
Preferably, the negative active material includes a silicon carbon material.
Preferably, the conductive agent comprises carbon black.
Preferably, the binder comprises CMC and/or SBR.
Preferably, the Ti-containing oxide solid electrolyte layer has a thickness of 2 to 5 μm, for example, 2.3 μm, 2.6 μm, 2.9 μm, 3.3 μm, 3.6 μm, 3.9 μm, 4.3 μm, 4.6 μm or 4.9 μm, and specific values therebetween, which are limited in space and for the sake of brevity, are not exhaustive of the invention to include the specific values within the stated ranges.
Preferably, the raw material for preparing the Ti oxide-containing solid electrolyte layer includes a Ti oxide-containing slurry.
Preferably, the Ti-containing oxide substance slurry comprises the following components in parts by weight: 80-95 parts of Ti-containing oxide solid electrolyte, 0.5-3 parts of binder and 15-70 parts of solvent.
The Ti-containing oxide may be 82 parts by weight, 84 parts by weight, 86 parts by weight, 88 parts by weight, 90 parts by weight, 92 parts by weight, or 94 parts by weight, and specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The binder may be present in an amount of 0.7 parts by weight, 0.9 parts by weight, 1.1 parts by weight, 1.3 parts by weight, 1.6 parts by weight, 1.9 parts by weight, 3.3 parts by weight, 3.6 parts by weight, or 3.9 parts by weight, and the specific values therebetween are not exhaustive for the purpose of brevity and clarity.
The solvent may be 20 parts by weight, 30 parts by weight, 40 parts by weight, 50 parts by weight, 60 parts by weight, or 65 parts by weight, and specific points therebetween are not exhaustive for the invention and are included for brevity.
Preferably, the binder comprises any one of polyvinylidene fluoride, CMC or SBR or a combination of at least two thereof.
Preferably, the solvent comprises N-methylpyrrolidone.
Preferably, the Ti-containing oxide includes any one of lithium titanium phosphate, lithium titanium aluminum phosphate, or lithium lanthanum titanate, or a combination of at least two thereof.
Preferably, the Ti-containing oxide has a particle size of 1 to 100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90nm, and specific values therebetween, are not exhaustive for the invention and are included for brevity.
Preferably, the Ti-containing oxide slurry is prepared by a method comprising the steps of:
(A1) Mixing a binder and a solvent to obtain a binder glue solution;
(A2) And (2) mixing the binder glue solution obtained in the step (A1) with the Ti-containing oxide to obtain the Ti-containing oxide slurry.
In a second aspect, the present invention provides a method for preparing the negative electrode plate according to the first aspect, where the method includes: and sequentially coating the preparation raw material of the active substance layer and the Ti-containing oxide slurry on the surface of the current collector to obtain the negative pole piece.
In a third aspect, the present invention provides a lithium ion battery, which includes the negative electrode plate, the positive electrode plate, the separator and the electrolyte solution described in the first aspect.
In a fourth aspect, the present invention provides a method for preparing the lithium ion battery according to the third aspect, wherein the method comprises the following steps:
(1) Laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) And (3) carrying out clamp formation on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
Preferably, the temperature of the aging in the step (2) is 35 to 65 ℃, for example, 38 ℃, 41 ℃, 45 ℃, 48 ℃, 51 ℃, 55 ℃, 58 ℃, 61 ℃ or 63 ℃, and the specific values therebetween are limited by space and for the sake of brevity, and the invention is not exhaustive and does not include the specific values included in the range, and more preferably 35 to 45 ℃.
Preferably, the aging time of step (2) is 70-74 h, such as 70.5h, 71h, 71.5h, 72h, 72.5h, 73h or 73.5h, and the specific values therebetween, which are limited by space and for the sake of brevity, the present invention is not exhaustive of the specific values included in the range.
Preferably, the method of forming the jig in step (3) comprises: the reaction is carried out at a temperature of 40 to 50 ℃ (e.g., 41 ℃, 42 ℃, 43 ℃, 44 ℃, 45 ℃, 46 ℃, 47 ℃, 48 ℃, or 49 ℃) and at a current of 0.01 to 0.5 ℃ (e.g., 0.05C, 0.1C, 0.15C, 0.2C, 0.25C, 0.3C, 0.35C, 0.4C, or 0.45C) for 4 to 25 hours (e.g., 9h, 13h, 15h, 17h, 19h, 21h, 23h, 24h, or 25 h), at a temperature of 30 to 40 ℃ (e.g., 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, or 39 ℃) and at a current of 0.5 to 2C (e.g., 0.7C, 0.8C, 0.9C, 1.3C, 1.5C, 1.7C, or 1.9C) for 10 to 100 hours (e.g., 10h, 20h, 30h, 70h, 60h, 90h, 100h, or the like). As a preferred technical solution of the present invention, the preparation method of the lithium ion battery provided by the present invention comprises: the lithium ion battery cathode plate is prepared by the steps of reacting for 4-25h at the temperature of 40-50 ℃ and the current of 0.01-0.5C and reacting for 10-100 h at the temperature of 30-40 ℃ and the current of 0.5-2C, and the step is matched with the cathode plate provided by the first aspect, so that the use amount of electrolyte in the lithium ion battery can be increased, and the dissolution of Mn ions in the cathode plate can be inhibited; the safety performance and the electrical performance of the lithium ion battery are further improved.
Preferably, the clamp is formed with a clamp pressure of 50-1000 kg, such as 100kg, 200kg, 300kg, 400kg, 500kg, 600kg, 700kg, 800kg or 900kg, and specific points therebetween, not exhaustive of the specific points included in the range for brevity and conciseness.
As a preferred technical scheme, the preparation method comprises the following steps:
(1) Laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) And (3) converting the lithium ion battery obtained in the step (2) into a lithium ion battery for 4-25h under the conditions of the temperature of 40-50 ℃ and the current of 0.01-0.5C, and converting the lithium ion battery into a lithium ion battery for 10-100 h under the conditions of the temperature of 30-40 ℃ and the current of 0.5-2C, so as to obtain the lithium ion battery.
In a fifth aspect, the present invention provides a use of the lithium ion battery according to the third aspect in the automotive field.
Compared with the prior art, the invention has the following beneficial effects:
(1) The negative pole piece provided by the invention comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged; through the design of the three-layer structure, each layer of structure is specially selected, so that when the negative pole piece is applied to the lithium ion battery, a layer of compact passivation film can be formed on the surface of the negative pole piece, the passivation film can avoid safety problems such as battery short circuit, explosion and combustion and the like caused by the fact that the lithium dendrite pierces the lithium ion battery diaphragm, and the safety performance of the lithium ion battery is improved.
(2) The negative pole piece and the preparation method of the lithium ion battery provided by the invention can inhibit the dissolution of Mn ions in the positive pole material, reduce the using amount of electrolyte and further improve the safety performance of the lithium ion battery.
(3) Specifically, the lithium ion battery prepared by the negative pole piece provided by the invention has the liquid retention capacity of 119-125 g, the internal resistance (DCR) of 1.28-1.3 m omega, the failure time of more than 2.2h at 130 ℃, the cycle performance of 2320-2503 weeks and the energy density of 280-291 Wh/kg.
Drawings
Fig. 1 is a schematic cross-sectional structure diagram of a negative electrode plate provided by the present invention, wherein 1-a current collector, 2-an active material layer and 3-a Ti-containing oxide solid electrolyte layer;
fig. 2 is a scanning electron microscope image of a negative electrode sheet after disassembly of the lithium ion battery provided in application example 1;
fig. 3 is a scanning electron microscope image of the composite separator after the lithium ion battery provided in application example 1 is disassembled;
fig. 4 is a scanning electron microscope image of a negative electrode tab after disassembly of the lithium ion battery provided in comparative application example 3;
fig. 5 is a scanning electron microscope image of the composite separator disassembled from the lithium ion battery provided in comparative application example 3.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Preparation example 1
The lithium aluminum titanium phosphate slurry comprises the following components in parts by weight:
the preparation method of the lithium aluminum titanium phosphate slurry provided by the preparation example comprises the following steps:
(1) Mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) And (2) mixing the binder glue solution obtained in the step (1) with lithium titanium aluminum phosphate to obtain the lithium titanium aluminum phosphate slurry.
Preparation example 2
The titanium lithium phosphate slurry comprises the following components in parts by weight:
the preparation method of the lithium titanium phosphate slurry provided by the preparation example comprises the following steps:
(1) Mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) And (2) mixing the binder glue solution obtained in the step (1) with lithium titanium phosphate to obtain the lithium titanium aluminum phosphate slurry.
Preparation example 3
The lanthanum lithium titanate slurry comprises the following components in parts by weight:
the preparation method of the lanthanum lithium titanate slurry provided by the preparation example comprises the following steps:
(1) Mixing CMC, SBR and NMP to obtain a binder glue solution;
(2) And (2) mixing the binder glue solution obtained in the step (1) with the lanthanum lithium titanate to obtain the lanthanum lithium titanate slurry.
Preparation example 4
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are sequentially arranged;
wherein, the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 μm, and the material is titanium aluminum lithium phosphate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 μm, and the materials are titanium aluminum lithium phosphate and aluminum oxide with the mass ratio of 1;
the thickness of the polyolefin layer is 9 μm, and the material is polyethylene (Hebei Jinli New energy science and technology Co., ltd., model SU 09);
the thickness of the second Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are lithium aluminum titanium phosphate and aluminum oxide with the ratio of 1;
the preparation method of the composite diaphragm provided by the preparation example comprises the following steps:
(1) Coating a material of a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer and a preparation raw material of a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer on two sides of the polyethylene layer respectively to obtain a composite layer;
(2) And (2) coating titanium aluminum lithium phosphate on the surface of the first Ti oxide-containing solid electrolyte/ceramic oxide collocation layer of the composite layer obtained in the step (1) to obtain the composite diaphragm.
Preparation example 5
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are sequentially arranged;
wherein the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 mu m, and the material is titanium lithium phosphate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 μm, and the materials are titanium lithium phosphate and aluminum oxide with the mass ratio of 1;
the thickness of the polyolefin layer is 9 μm, and the material is polyethylene (Hebei Jinli New energy science and technology Co., ltd., model SU 09);
the thickness of the second Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are titanium lithium phosphate and alumina with the mass ratio of 1;
the preparation method of the composite separator provided in this preparation example is the same as that of preparation example 4.
Preparation example 6
A composite diaphragm comprises a Ti oxide-containing solid electrolyte layer, a first Ti oxide-containing solid electrolyte/ceramic oxide matching layer, a polyolefin layer and a second Ti oxide-containing solid electrolyte/ceramic oxide matching layer which are arranged in sequence;
wherein, the thickness of the Ti-containing oxide solid electrolyte layer is 1.5 μm, and the material is lanthanum lithium titanate;
the thickness of the first Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2 μm, and the materials are lanthanum lithium titanate and aluminum oxide with the mass ratio of 1;
the thickness of the polyolefin layer is 9 μm, and the material is polyethylene (Hebei Jinli New energy science and technology Co., ltd., model SU 09);
the thickness of the second Ti-containing oxide solid electrolyte/ceramic oxide matching layer is 2.5 mu m, and the materials are lanthanum lithium titanate and aluminum oxide with the mass ratio of 1;
the preparation method of the composite separator provided in the preparation example is the same as that of preparation example 4.
Example 1
A schematic cross-sectional structure of a negative electrode sheet is shown in fig. 1, and includes a current collector 1, an active material layer 2, and a Ti-containing oxide solid electrolyte layer 3;
wherein, the current collector 1 is a copper foil with the thickness of 8 μm;
the thickness of the active material coating layer 2 is 175 μm, and the raw materials are active material slurry (the preparation method includes mixing a silicon carbon material, carbon black, a binder (CMC and SBR in a mass ratio of 1.3;
the thickness of the solid electrolyte layer 3 was 3 μm, and a titanium aluminum lithium phosphate slurry (preparation example 1) was prepared as a raw material;
the preparation method of the negative electrode plate provided by the embodiment includes: and sequentially coating active substance slurry and titanium aluminum lithium phosphate slurry on the surface of the copper foil to obtain the negative pole piece.
Example 2
A negative electrode sheet differing from example 1 only in that the lithium titanium phosphate slurry obtained in preparation example 2 was used instead of the lithium aluminum titanium phosphate slurry obtained in preparation example 1 as a raw material for preparing a solid electrolyte layer, and the other structures, parameters and preparation methods were the same as those of example 1.
Example 3
A negative electrode sheet differing from example 1 only in that the lanthanum lithium titanate slurry obtained in production example 3 was used instead of the titanium aluminum lithium phosphate slurry obtained in production example 1 as a raw material for producing a solid electrolyte layer, and the other structures, parameters and production methods were the same as in example 1.
Example 4
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 2 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Example 5
A negative electrode sheet was different from example 1 in that the thickness of the solid electrolyte layer was 5 μm, the thickness of the active material coating was 175 μm, and other structures, parameters and preparation methods were the same as example 1.
Example 6
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 1 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Example 7
A negative electrode plate was distinguished from example 1 in that the thickness of the solid electrolyte layer was 6 μm, the thickness of the active material coating was 175 μm, and the other structures, parameters and preparation methods were the same as in example 1.
Comparative example 1
A negative electrode sheet was distinguished from production example 1 only in that no solid electrolyte layer was provided, the thickness of the active material coating was 175 μm, and the other structures, parameters and production methods were the same as in production example 1.
Application example 1
A lithium ion battery comprises a positive pole piece, a negative pole piece, a composite diaphragm and electrolyte;
the positive electrode plate is obtained by coating positive electrode slurry (NMC 811, carbon black and PVDF in a mass ratio of 95 2 ；
Negative electrode sheet (example 1);
composite separator (preparation example 4);
the electrolyte comprises EC, PC, EMC, VC and PS in a volume ratio of 35 6 ；
The preparation method of the lithium ion battery provided by the application example comprises the following steps:
(1) Laminating the positive pole piece, the negative pole piece and the diaphragm in a Z shape (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) And (3) carrying out formation for 23h at 45 ℃ under the current of 0.02C on the lithium ion battery obtained in the step (2), carrying out clamping for 10 weeks at 35 ℃ under the current of 1C for 30h, carrying out clamp pressure of 750kg, degas, and carrying out normal-temperature aging to obtain the lithium ion battery.
Application example 2
An application example 1 of a lithium ion battery is different in that the negative electrode sheet obtained in example 2 is used to replace the negative electrode sheet obtained in example 1, the composite separator obtained in preparation example 5 is used to replace the composite separator obtained in preparation example 3, and other structures, parameters and preparation methods are the same as those in application example 1.
Application example 3
An application example 1 of a lithium ion battery is different in that the negative electrode sheet obtained in example 3 is used to replace the negative electrode sheet obtained in example 1, the composite separator obtained in preparation example 6 is used to replace the composite separator obtained in preparation example 3, and other structures, parameters and preparation methods are the same as those in application example 1.
Application example 4
The difference of application example 1 of the lithium ion battery is that the negative electrode plate obtained in example 4 is used to replace the negative electrode plate obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 5
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 5 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 6
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 6 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Application example 7
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in example 7 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Comparative application example 1
The difference of application example 1 of the lithium ion battery is that the negative electrode sheet obtained in comparative example 1 is used to replace the negative electrode sheet obtained in example 1, and other structures, parameters and preparation methods are the same as those of application example 1.
Comparative application example 2
A lithium ion battery which is different from the application example 1 only in that the preparation method comprises the following steps:
(1) Laminating the positive pole piece, the negative pole piece and the diaphragm in a zigzag manner (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) And (3) carrying out non-pressure formation, degas and normal-temperature aging on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
Comparative application example 3
A lithium ion battery comprises a positive pole piece, a negative pole piece, a composite diaphragm and electrolyte;
wherein, the positive pole piece is formed by coating positive slurry (quality) on the surface of an aluminum foilNMC811, carbon black and PVDF at a ratio of 95 2 ；
Negative electrode sheet (comparative example 1);
composite separator (preparation example 4);
the electrolyte comprises EC, PC, EMC, VC and PS in a volume ratio of 35 6 ；
The preparation method of the lithium ion battery obtained by the comparative application example comprises the following steps:
(1) Laminating the positive pole piece, the negative pole piece and the diaphragm in a Z shape (30 layers of the positive pole piece and 31 layers of the negative pole piece), and packaging with aluminum plastic to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1) at 85 ℃ for 15h, injecting electrolyte, pre-charging, aging at 45 ℃ for 72h, and forming to obtain a formed lithium ion battery;
(3) And (3) carrying out non-pressure formation, degas and normal-temperature aging on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery.
And (4) performance testing:
(1) And (3) appearance observation: observing the disassembled composite diaphragm and negative electrode plate of the lithium ion battery provided in the corresponding example 1 and the comparative application example 3 by using a scanning electron microscope (SU 8100 scanning electron microscope, hitachi high and New technology corporation, japan column type Co., ltd.), wherein the test results are shown in FIGS. 2 to 5;
wherein, fig. 2 is a scanning electron microscope image of the disassembled negative pole piece of the lithium ion battery obtained in application example 1; FIG. 3 is a scanning electron microscope image of the disassembled composite diaphragm of the lithium ion battery obtained in application example 1; as can be seen from fig. 2 and 3, the composite diaphragm provided by the present invention and the surface of the negative electrode plate form an integrated film, and a dense passivation layer is formed on both the surface of the negative electrode plate and the surface of the composite diaphragm; the compact layer is a compact passivation layer formed by the reaction of Ti atoms in LATP and Li under the electric potential close to 0V; fig. 4 is a scanning electron microscope image of a negative electrode plate obtained after a lithium ion battery is disassembled in comparative application example 3, fig. 5 is a scanning electron microscope image of a composite diaphragm obtained after the lithium ion battery is disassembled in comparative application example 3, and as can be seen from fig. 4 and fig. 5, the lithium ion battery obtained by adopting a common negative electrode plate and a traditional lithium ion battery preparation method does not have the passivation film on the surface of the diaphragm of the negative electrode plate after disassembly, so that the compact film formed by the composite diaphragm provided by the invention can prevent lithium dendrites from permeating into a base film from the positive electrode side and consume dendritic lithium, and further, safety accidents such as battery short circuit, explosion and the like caused by the fact that the lithium dendrites pierce through the lithium ion battery diaphragm are avoided.
(2) Liquid retention amount, internal resistance, 130 ℃ failure time: fully filling the lithium ion battery with a 1C constant current and a constant voltage, standing for 3h, heating the lithium ion battery in an oven at the temperature of 130 ℃, increasing the temperature from room temperature to 130 ℃ at the heating rate of 5 ℃/min, keeping the temperature at 130 ℃ for 3h, and then testing;
(3) Cycle performance: cycling the lithium ion battery at 45 deg.C for a period of time recording the capacity below 80% SOH.
(4) Energy density: energy of the first cycle of the lithium ion battery/mass of the lithium ion battery;
the lithium ion batteries obtained in the application examples 1 to 7 and the comparative application examples 1 to 3 were tested according to the above test methods (2) and (3), and the test results are shown in table 1:
TABLE 1
As can be seen from the data in table 1: the lithium ion battery prepared by the negative pole piece provided by the invention has the liquid retention capacity of 119-125 g, the internal resistance (DCR) of 1.28-1.3 m omega, the failure time of more than 2.2h at 130 ℃, the cycle performance of 2320-2503 weeks and the energy density of 280-291 Wh/kg.
Compared with application example 1 and application example 1, the lithium ion battery obtained by using the negative electrode plate provided by the invention has the advantages of smaller DCR, smaller usage amount of electrolyte retention, higher energy density and more excellent cycle performance.
Comparing application example 1 with comparative application examples 2 to 3, it can be found that without the preparation method provided by the present invention, the obtained lithium ion battery has high internal resistance, poor cycle performance, high electrolyte retention capacity, and low energy density, and the lithium ion battery with improved performance cannot be obtained.
Further comparing application examples 1 and 4 to 7, it can be found that when the thickness of the Ti-containing oxide solid electrolyte layer is too low (application example 6), the reduction effect on the electrolyte is weakened, and the formed passivation film is thin, so that the lithium ion battery is thermally out of control within 2.2 hours; when the thickness of the Ti-containing oxide solid electrolyte layer is too large (application example 7), the mass energy density of the lithium ion battery is reduced
In summary, for the present invention, the specific method for preparing the lithium ion battery and the specific cathode are key to improve the performance of the battery, and only under the specific process conditions of the present invention, the passivation layer can be effectively formed, thereby effectively improving the safety and cycle performance of the battery.
The applicant states that the invention is described by the above examples to a negative electrode sheet and its preparation method and application, but the invention is not limited to the above process steps, that is, it is not meant that the invention must rely on the above process steps to implement. It will be apparent to those skilled in the art that any modifications to the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific forms, etc., are within the scope and disclosure of the present invention.
Claims (18)
1. A lithium ion battery is characterized by comprising a negative pole piece, a positive pole piece, a diaphragm and electrolyte;
the negative pole piece comprises a current collector, an active substance layer and a Ti-containing oxide solid electrolyte layer which are sequentially arranged;
the thickness of the Ti-containing oxide solid electrolyte layer is 2-5 mu m;
the raw materials for preparing the Ti-containing oxide solid electrolyte layer comprise Ti-containing oxide slurry, wherein the Ti-containing oxide slurry comprises the following components in parts by weight: 80-95 parts of Ti-containing oxide solid electrolyte, 0.5-3 parts of binder and 15-70 parts of solvent;
the Ti-containing oxide solid electrolyte comprises any one of titanium lithium phosphate, titanium aluminum lithium phosphate or lanthanum lithium titanate or a combination of at least two of the titanium lithium phosphate, the titanium aluminum lithium phosphate and the lanthanum lithium titanate;
the lithium ion battery is prepared by the following method:
(1) Laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) Carrying out clamp formation on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery;
the method for forming the clamp in the step (3) comprises the following steps: the temperature is 40-50 ℃ and the current is 0.01-0.5C, the reaction time is 4-25h, the temperature is 30-40 ℃ and the current is 0.5-2C, the reaction time is 10-100 h, and the formation of the clamp is finished;
the pressure of the clamp formed by the clamp is 50-1000 kg.
2. The lithium ion battery of claim 1, wherein the negative electrode tab has a thickness of 80-200 μm.
3. The lithium ion battery of claim 1, wherein the current collector comprises a copper foil.
4. The lithium ion battery according to claim 1, wherein the thickness of the active material layer is 70 to 190 μm.
5. The lithium ion battery of claim 1, wherein the material of the active material coating comprises a combination of a negative electrode active material, a conductive agent, and a binder.
6. The lithium ion battery of claim 5, wherein the negative active material comprises a silicon carbon material.
7. The lithium ion battery of claim 5, wherein the conductive agent comprises carbon black.
8. The lithium ion battery of claim 5, wherein the binder comprises CMC and/or SBR.
9. The li-ion battery of claim 1, wherein the binder comprises any one of polyvinylidene fluoride, CMC, or SBR, or a combination of at least two thereof.
10. The lithium ion battery of claim 1, wherein the solvent comprises N-methylpyrrolidone.
11. The lithium ion battery according to claim 1, wherein the Ti-containing oxide solid electrolyte has a particle size of 1 to 100nm.
12. The lithium ion battery of claim 1, wherein the Ti-containing oxide slurry is prepared by a method comprising the steps of:
(A1) Mixing a binder and a solvent to obtain a binder glue solution;
(A2) And (2) mixing the binder glue solution obtained in the step (A1) with the Ti-containing oxide to obtain the Ti-containing oxide slurry.
13. The lithium ion battery of claim 1, wherein the negative electrode sheet is prepared by a method comprising: and sequentially coating the preparation raw material of the active substance layer and the Ti-containing oxide slurry on the surface of the current collector to obtain the negative pole piece.
14. A method for preparing a lithium ion battery according to any one of claims 1 to 13, comprising the steps of:
(1) Laminating and packaging the positive pole piece, the negative pole piece and the diaphragm to obtain an initial lithium ion battery;
(2) Baking the initial lithium ion battery obtained in the step (1), injecting electrolyte, pre-charging, aging and forming to obtain a formed lithium ion battery;
(3) Carrying out clamp formation on the formed lithium ion battery obtained in the step (2) to obtain the lithium ion battery;
the method for forming the clamp in the step (3) comprises the following steps: the temperature is 40-50 ℃ and the current is 0.01-0.5 ℃ for 4-25h, the temperature is 30-40 ℃ and the current is 0.5-2 ℃ for 10-100 h, and the clamp formation is completed;
the pressure of the clamp formed by the clamp is 50-1000 kg.
15. The method according to claim 14, wherein the temperature of the aging in the step (2) is 35 to 65 ℃.
16. The method according to claim 15, wherein the aging temperature in the step (2) is 35 to 45 ℃.
17. The method of claim 14, wherein the aging time of step (2) is 70 to 74 hours.
18. Use of a lithium ion battery according to any of claims 1 to 13 in the automotive field.
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