CN115632123A - All-solid-state lithium battery and preparation method thereof - Google Patents
All-solid-state lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an all-solid-state lithium battery and a preparation method thereof, belonging to the field of solid-state lithium batteries. The cathode of the all-solid-state lithium battery comprises LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE, super-P and current-collecting carbon-coated aluminum foil; the electrolyte comprises Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 CMC and PTFE; the anode is an In/Li alloy foil and a current-collecting copper foil. Firstly, respectively preparing a cathode, an electrolyte membrane and an anode, then alternately laminating the cathode, the electrolyte membrane and the anode for multiple layers, welding tabs, and then packaging by using an aluminum plastic film to obtain the all-solid-state lithium battery. The invention can give full play to spinel LiNi 0.5 Mn 1.5 O 4 And olivine LiFe 0.8 Mn 0.2 PO 4 The interface and structural stability of the cathode material are obviously improved under the synergistic effect of the two cathode materials; the obtained all-solid-state lithium battery has the advantages of good cycle performance, good rate performance and the like.
Description
Technical Field
The invention belongs to the field of solid-state lithium batteries, and particularly relates to a solid-state lithium battery and a preparation method thereof.
Background
The lithium ion battery has the advantages of high energy density, small self-discharge, no memory effect, long cycle life and the like, so that the lithium ion battery is widely applied to the fields of electric vehicles, large-scale energy storage, aerospace and the like, and plays an important role in the fields of civil life, military and the like. The lithium ion battery mainly comprises electrode plates, electrolyte, a diaphragm, a shell and the like. The electrolyte contains organic solvents such as low-flash-point and flammable carbonic ester, so that vicious safety accidents such as combustion and even explosion are easily caused, and the development and the application of the lithium ion battery in the field of high-energy-density energy storage are undoubtedly limited. The proposal of the solid-state concept of the electrolyte is expected to fundamentally eliminate a series of potential safety hazards caused by the traditional electrolyte and further improve the energy density of the lithium ion battery. Solid-state electrolytes can be divided into organic (polymer) and inorganic (oxide or sulfide) solid-state electrolytes. In 2012, bolore has implemented commercial use of polymer all solid-state batteries in france. The polymer all-solid-state battery dissolves LiFSI lithium salt in polyethylene oxide (PEO), so that the polymer all-solid-state battery is high in safety and long in cycle life. However, because the oxidation potential of the PEO material is only 3.8V and can only be matched with low-voltage positive electrode materials such as lithium iron phosphate, the cell energy density is only 220Wh/kg. PEO has high ionic conductivity under the environment of 60-85 ℃, so a heating device is required to be arranged for correcting the PEOThe energy density of the system level is only 110-130Wh/kg in normal work, the safety of the polymer is not good, and the phenomena of good thermal stability of sulfide and oxide, and ignition and combustion can occur at high temperature. Sulfide materials are the highest ionic conductivity systems at room temperature and therefore have received extensive attention and research, mainly involving glassy phase and glassy ceramic phase materials (Li) 2 S-P 2 S 5 Etc.), thio-fast ion conductors (thio-LISICON), LPSCl, LGPS series, and layered series. The LGPS (lithium germanium phosphorus sulfur) which is first reported in 2011 has ultrahigh ionic conductivity of up to 12mS/cm at room temperature, and even exceeds part of organic electrolyte. However, the sulfide is liable to undergo an interfacial side reaction with metallic lithium and the positive electrode material, resulting in poor interface stability. The oxide material electrolyte material mainly includes a garnet structure (LLZO), a NASICON structure (lag and LATP), a perovskite structure (LLTO), and the like. The oxide is essentially ceramic material, and has excellent electrochemical and mechanical stability, but ceramic particles are very hard, and the material is very easy to crack, so that a large-area or multilayer cell is difficult to prepare. In addition, the ceramic particles have a serious solid-solid contact problem with the anode and the cathode, and the interface lithium conducting performance is poor.
The all-solid-state lithium battery mainly comprises four parts, namely a cathode, an anode, an electrolyte and an auxiliary material. CN106876707A reports a lithium ion battery assembled by lamination mode, the main component in the cathode is Li 3 V 2 (PO 4 ) 3 And LiM 2 (PO 4 ) 3 A base compound, the main component of the electrolyte being LiM 2 (PO 4 ) 3 A base compound, wherein M = one or more of Ge, ti, hf, al, si, V, sc or Zr. Wherein the V element has larger toxicity, and two cathode materials Li 3 V 2 (PO 4 ) 3 And LiM 2 (PO 4 ) 3 The specific capacity of the catalyst is lower. CN109428053A reports a cathode sheet for an all-solid-state lithium battery, which contains Li 2 Lithium electrolyte salts such as S and the like, and olivine-structured cathode materials and the like. The cathode material of olivine structure has low ionic and electronic conductivity, and is made of olivine structure aloneWhen the material is used as a cathode active material of an all-solid-state lithium battery, the capacity of the battery is low, and the rate capability is poor. CN101013761A, CN113659196A each report a sulfide electrolyte for an all-solid lithium battery, the main component of which contains amorphous Li 2 S and other sulfide materials. These sulfide electrolytes, although possibly having high ionic conductivity, are susceptible to side reactions with the cathode active material and have poor interface stability. CN114824457a reports a Li/Si alloy negative electrode for all solid-state lithium battery and a sulfide electrolyte. However, si materials have low electron conductivity, and Li/Si alloys are susceptible to side reactions with sulfide electrolytes, and have poor interface stability. CN114665068A reports a Li/Al alloy cathode for an all-solid-state lithium battery, but the Li/Al alloy has high lithium removal potential, and the surface of Al metal is often accompanied by dense Al 2 O 3 The process is complex and difficult in the process of actually preparing the Li/Al alloy. CN113140731A reports a Li-based 1- z Al z M 2-z (PO4) 3 (M = one or more of Ti, ge and Zr) electrolyte and a carbon cathode, but the carbon material and the sulfide electrolyte have side reaction and are not suitable for the all-solid-state lithium battery of the sulfide electrolyte system.
Disclosure of Invention
The invention aims to provide an all-solid-state lithium battery and a preparation method thereof so as to achieve the purpose of improving the electrochemical performance of the solid-state lithium battery.
In order to solve the above technical problems, according to an aspect of the present invention, there is provided an all solid-state lithium battery including a cathode, an electrolyte, and an anode,
the cathode comprises LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE, super-P and current-collecting carbon-coated aluminum foil;
the electrolyte comprises Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 CMC and PTFE;
the anode is an In/Li alloy foil and a current-collecting copper foil.
Further, liNi 0.5 Mn 1.5 O 4 The particle diameter of the material particles is 5-50 mu m, liFe 0.8 Mn 0.2 PO 4 The particle size of the material particles is 10-200nm.
Further, liNi in the cathode 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 The mass ratio of (3:7) - (7:3); in the cathode component except the carbon-coated aluminum foil of the current collector, li 2 MnP 2 O 7 The mass fractions of PTFE and Super-P are 0.5-10%.
Further, li in the electrolyte 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 The mass ratio of (3:7) - (7:3); the mass fractions of CMC and PTFE in the electrolyte are both 0.5-10%.
Furthermore, the mass fraction of In the anode In/Li alloy foil is 70-95%.
Further, the auxiliary material is included, and the auxiliary material comprises a tab and an aluminum-plastic film.
According to another aspect of the present invention, there is provided a method for preparing the above all-solid-state lithium battery, comprising the steps of:
firstly, respectively preparing a cathode, an electrolyte membrane and an anode, then alternately laminating the cathode, the electrolyte membrane and the anode for multiple layers, welding tabs, and then packaging by using an aluminum-plastic film to obtain the all-solid-state lithium battery;
wherein, the preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE and Super-P are put in a stirrer according to the designed stoichiometry and are uniformly mixed, then the mixture is repeatedly hot-pressed into an electrode film in a roller press with a heating function, and finally the electrode film is stuck on two surfaces of a current collector carbon-coated aluminum foil and is hot-pressed and solidified to obtain the cathode of the all-solid-state battery;
the preparation process of the electrolyte membrane comprises the following steps: mixing Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 And dispersing CMC and PTFE in acetonitrile, stirring and mixing uniformly, evaporating the solvent to obtain a solid mixture, and repeatedly hot-pressing the solid mixture in a roller press with a heating function to form a membrane, thus obtaining the electrolyte membrane.
Further, the preparation process of the anode comprises the following steps: and covering the In/Li alloy foil on two sides of the copper foil, and rolling and shaping by using a roller press In an anhydrous and oxygen-free environment to obtain the anode of the all-solid-state lithium battery.
Further, in the preparation process of the anode and the electrolyte membrane, the heating temperature of the heating roller press is 60-95 ℃.
Further, the thickness of the cathode is 150-220 μm, the thickness of the electrolyte membrane is 60-120 μm, and the thickness of the anode is 15-30 μm.
In the present invention, liNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 Is a cathode active material, liFe 0.8 Mn 0.2 PO 4 Dispersed in LiNi 0.5 Mn 1.5 O 4 The surface of the material can simultaneously protect LiNi 0.5 Mn 1.5 O 4 Inhibition of LiNi 0.5 Mn 1.5 O 4 And side reactions with the electrolyte. Li 2 MnP 2 O 7 Can obviously improve LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 The structural stability and the cycle performance of the composite cathode. Oxide electrolyte Li 7 La 3 Zr 1.6 Ta 0.4 O 12 And sulfide electrolyte Li 20 Si 3 P 3 S 23 The compounding of Cl can effectively avoid the space charge layer effect on a solid-solid interface, and the effects of high ionic conductivity, high mechanical strength and high thermal stability are realized.
The In metal improves the potential of the negative electrode, obviously improves the stability between the anode and the electrolyte and avoids the side reaction of the anode and the electrolyte.
In conclusion, the all-solid-state battery of the invention can fully develop spinel LiNi 0.5 Mn 1.5 O 4 And olivine LiFe 0.8 Mn 0.2 PO 4 The interface and structural stability of the cathode material are obviously improved under the synergistic effect of the two cathode materials; simultaneously, the advantages of high conductivity of the sulfide electrolyte and high stability of the oxide electrolyte are exerted, and the defects that the anode is easy to generate dendrite and has side reaction with the electrolyte interface and the like are avoided. The all-solid-state battery has the advantages of good cycle performance, good rate performance and the like. Meanwhile, the all-solid-state battery is simple in preparation process and easy to realize industrial production.
Drawings
Fig. 1 is a cycle performance curve of all solid-state lithium batteries prepared according to example 1 of the present invention and corresponding comparative example.
Fig. 2 is a graph showing rate performance of all solid-state lithium batteries prepared in example 2 of the present invention and corresponding comparative examples.
Fig. 3 is a surface temperature variation curve of the all solid-state lithium battery prepared in example 3 of the present invention in a needle punching experiment.
Detailed Description
An exemplary embodiment of the present invention provides an all-solid-state lithium ion battery including a cathode, an electrolyte, an anode, and an auxiliary material.
The cathode comprises LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE (polytetrafluoroethylene), super-P (a conductive carbon black) and current collector carbon coated aluminum foil. The electrolyte comprises Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 CMC and PTFE. The anode is an In/Li alloy foil and a current-collecting copper foil. The auxiliary materials comprise a tab and a battery outer packaging aluminum-plastic film.
Among the above cathode materials, liNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 Is a cathode active material, liFe 0.8 Mn 0.2 PO 4 Dispersed in LiNi 0.5 Mn 1.5 O 4 The surface of the material is simultaneously protectedLiNi 0.5 Mn 1.5 O 4 Inhibition of LiNi 0.5 Mn 1.5 O 4 And side reactions with the electrolyte.
Li 2 MnP 2 O 7 Is a cathode material modifier and has excellent chemical stability. The applicant found in earlier studies that small amounts of Li were added to the cathode 2 MnP 2 O 7 Can obviously improve LiNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 The composite cathode material has stable structure and cycle performance, reduces the interface impedance between the cathode material and the electrolyte, and obviously improves the electrochemical performance of the solid-state lithium battery.
PTFE is a binder, super-P is a conductive agent, and PTFE and Super-P in proper proportion can inhibit the performance deterioration of the active material caused by volume expansion and contraction, reduce the ohmic resistance and electrochemical polarization of the electrode and improve the electrochemical performance of the cathode material.
The carbon-coated aluminum foil is used as the cathode current collector, so that the bonding effect between the cathode and the aluminum foil current collector can be obviously improved, and the interface resistance of the cathode and the aluminum foil current collector is reduced.
In the aspect of the electrolyte, the active ingredient of the electrolyte is Li 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 CMC is the thickener and binder, PTFE is the binder.
Sulfide electrolyte Li 20 Si 3 P 3 S 23 High Cl ion conductivity, oxide electrolyte Li 7 La 3 Zr 1.6 Ta 0.4 O 12 High mechanical strength and thermal stability. The compounding of the oxide and the sulfide electrolyte can effectively avoid the space charge layer effect on a solid-solid interface, and realize the effects of high ionic conductivity, high mechanical strength and high thermal stability. In a preferred embodiment, li 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 The mass ratio of (a) is 3:7-7:3, for example: 3:7, 4:6, 5:5, 6:4, 7:3.
In the aspect of anode materials, the In/Li alloy electrode and the electrolyte have good chemical stability and electrochemical stability, and are soft In texture, so that the interface impedance can be effectively reduced, and the ion migration rate and the charge-discharge efficiency can be improved. In a preferred embodiment, the mass fraction of In the anode In/Li alloy foil is 70-95%, for example: 70%, 72%, 75%, 76%, 80%, 83%, 85%, 87%, 90%, 93%, 95%.
In the present invention, liNi 0.5 Mn 1.5 O 4 The grain size of the material is micron-sized, and the grain size range is 5-50 mu m; liFe 0.8 Mn 0.2 PO 4 The particle size is nano-scale, and the particle size range is 10-200nm. In the preparation process of the cathode, nanoscale LiFe 0.8 Mn 0.2 PO 4 For micron-sized LiNi 0.5 Mn 1.5 O 4 Complete and uniform coating is realized, and nano LiFe 0.8 Mn 0.2 PO 4 Can effectively inhibit LiNi 0.5 Mn 1.5 O 4 And an electrolyte material, and enhance LiNi 0.5 Mn 1.5 O 4 The electrochemical stability of the cathode material is improved, and the electrochemical performance of the two cathode materials is improved synergistically. In a preferred embodiment, liNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 The mass ratio of (a) to (b) is 3:7-7:3, for example: 3:7, 4:6, 5:5, 6:4, 7:3.
Li 2 MnP 2 O 7 PTFE, super-P and CMC are all inactive materials, and the great increase of the content can cause the reduction of the specific capacity of the material. Therefore, the content of each component needs to be optimized so as to achieve the purpose of giving consideration to the rate capability, the cycle performance and the specific capacity of the composite material. In a preferred embodiment, li 2 MnP 2 O 7 The mass fractions of PTFE and Super-P in the cathode (except for the current collector carbon-coated aluminum foil) are all 0.5-10%. The mass fractions of CMC and PTFE in the electrolyte are both 0.5-10%.
Another exemplary embodiment of the present invention provides a method for manufacturing the above all solid-state lithium battery.
Firstly, respectively preparing a cathode, an electrolyte membrane and an anode, then alternately laminating and arranging the cathode, the electrolyte membrane and the anode for multiple layers, welding tabs, and then packaging by using an aluminum plastic film to obtain the all-solid-state lithium battery.
The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 And PTFE and Super-P are put into a high-shear mixer according to the designed stoichiometry and are uniformly mixed, then the mixture is repeatedly hot-pressed into an electrode film in a roller press with a heating function, and finally the electrode film is adhered to two surfaces of an aluminum foil and is hot-pressed and solidified to obtain the cathode of the all-solid-state battery.
Preparation process of the electrolyte membrane: mixing Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 And dispersing CMC and PTFE in acetonitrile, stirring and mixing uniformly, evaporating the solvent to obtain a solid mixture, and repeatedly hot-pressing the solid mixture in a roller press with a heating function to form a membrane, thus obtaining the electrolyte membrane. The liquid-phase membrane preparation method using acetonitrile as a dispersion liquid, CMC as a thickening agent and PTFE as a binder can realize highly uniform mixing of two electrolytes, remarkably improve the membrane forming quality of the electrolytes on the premise of not reducing the ionic conductivity of the electrolytes, and exert the best performance of the two electrolytes.
And in the preparation process of the cathode and the electrolyte membrane, the heating temperature of the heating roller press is 60-95 ℃.
The preparation process of the anode comprises the following steps: and covering the In/Li alloy foil on two sides of the copper foil, and rolling and shaping by using a roller press In an anhydrous and oxygen-free environment to obtain the anode of the all-solid-state lithium battery.
After rolling and shaping, the thickness of the cathode is 150-220 μm, the thickness of the electrolyte membrane is 60-120 μm, and the thickness of the anode is 15-30 μm.
By adopting the preparation method of the invention, liNi can be developed 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 The synergistic effect of the two cathode active materials exerts the advantages of high ionic conductivity of sulfide electrolyte and high mechanical strength and high thermal stability of oxide electrolyte, and reduces the grain boundary impedance of the cathode materialAnd interface charge transfer resistance in the all-solid-state battery, the interface stability and the charge-discharge efficiency of the all-solid-state battery are obviously improved, and the multiplying power and the cycle performance of the all-solid-state lithium battery are effectively improved.
The claimed solution is further illustrated by the following examples. However, the examples and comparative examples are intended to illustrate the embodiments of the present invention without departing from the scope of the subject matter of the present invention, and the scope of the present invention is not limited by the examples. Unless otherwise specifically indicated, the materials and reagents used in the present invention are available from commercial products in the art.
Example 1
(1) The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 Uniformly mixing according to the mass ratio of 6:4 to obtain a mixture A1, and mixing the mixture A1 with Li 2 MnP 2 O 7 And placing PTFE and Super-P in a high-shear mixer according to the mass ratio of 87.5 to 0.5.
(2) Preparation process of the electrolyte membrane: mixing Li 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 Uniformly mixing the materials according to a mass ratio of 3:7 to obtain a mixture B1, dispersing the mixture B1, CMC and PTFE in acetonitrile according to a mass ratio of 93.5.
(3) The preparation process of the anode comprises the following steps: and (3) coating the In/Li alloy foil with the In/Li mass ratio of 7:3 on two sides of the copper foil, and rolling and shaping by using a roller press In an anhydrous and oxygen-free environment to obtain the anode of the all-solid-state lithium battery, wherein the shaping thickness is 30 mu m. And (3) alternately stacking and arranging a plurality of cathodes, electrolytes and anodes, welding tabs, and packaging with an aluminum plastic film to obtain the all-solid-state lithium battery, wherein the total solid-state lithium battery is marked as 1-a.
To illustrate the synergistic effect among three lithiates in the cathode material of the present invention, the cathode material was separately assembled without adding LiNi 0.5 Mn 1.5 O 4 Without addition of LiFe 0.8 Mn 0.2 PO 4 And no addition of Li 2 MnP 2 O 7 The all solid-state lithium batteries of (1) are respectively labeled as 1-b, 1-c and 1-d.
Comparative examples 1 to 1
(1) The preparation process of the cathode comprises the following steps: mixing LiFe 0.8 Mn 0.2 PO 4 With Li 2 MnP 2 O 7 And placing PTFE and Super-P in a high-shear mixer according to the mass ratio of 87.5 to 0.5.
Steps (2) and (3) were the same as in example 1 to obtain LiNi without addition 0.5 Mn 1.5 O 4 The all solid-state lithium battery of (1), denoted by 1-b.
Comparative examples 1 to 2
(1) The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 With Li 2 MnP 2 O 7 And placing PTFE and Super-P in a high-shear mixer according to the mass ratio of 87.5 to 0.5.
Steps (2) and (3) were performed in the same manner as in example 1 to obtain LiFe without addition 0.8 Mn 0.2 PO 4 The all solid-state lithium battery of (1), labeled 1-c.
Comparative examples 1 to 3
(1) The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 According to 6:4The mixture A1, PTFE and Super-P are placed in a high-shear mixer according to the mass ratio of 88 to 10 to be uniformly mixed, then the mixture A1, PTFE and Super-P are repeatedly hot-pressed into an electrode film at 60 ℃ in a roller press with a heating function, finally the electrode film is adhered to two surfaces of a current collector carbon-coated aluminum foil, and the cathode sheet of the all-solid-state battery can be obtained after hot-pressing solidification to the thickness of 180 mu m.
Steps (2) and (3) were carried out in the same manner as in example 1 to obtain a lithium compound without addition of Li 2 MnP 2 O 7 The all solid-state lithium battery of (1) is labeled as 1-d.
The four all-solid batteries obtained in example 1, comparative examples 1 to 2 and comparative examples 1 to 3 were subjected to a cycle performance test at a charge and discharge current of 1A in a range of 3.5 to 5V, and comparative data are shown in fig. 1 and table 1, which shows that the all-solid battery 1-a obtained in example 1 of the present invention has significantly higher discharge capacity and cycle capacity retention rate. At the same time, it also shows that three lithiates in the cathode material can exert good synergistic effect.
TABLE 1 electrochemical performance data for four all solid-state lithium batteries prepared in inventive example 1
| Type of battery | 1-a | 1-b | 1-c | 1-d |
| First discharge capacity (Ah) | 2.10 | 2.00 | 1.96 | 2.10 |
| Discharge capacity at 50 th cycle (Ah) | 2.03 | 1.8 | 1.76 | 1.78 |
| Capacity retention (%) at 50-week cycle | 96.7 | 90.0 | 89.8 | 84.8 |
Example 2
(1) The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 Uniformly mixing the materials according to the mass ratio of 3:7 to obtain a mixture A2, and mixing the mixture A2 with Li 2 MnP 2 O 7 And PTFE and Super-P are placed in a high-shear mixer according to the mass ratio of 85.5.
(2) The preparation process of the electrolyte membrane comprises the following steps: mixing Li 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 Uniformly mixing the materials according to a mass ratio of 1:1 to obtain a mixture B2, dispersing the mixture B2, CMC and PTFE in acetonitrile according to a mass ratio of 92.5The thickness of the resulting electrolyte membrane was 60 μm, and an electrolyte membrane was obtained.
(3) The preparation process of the anode comprises the following steps: and (3) coating In/Li alloy foils with the In/Li mass ratio of 95. And (3) alternately stacking and arranging a plurality of layers of cathodes, electrolytes and anodes, welding tabs, and packaging by using an aluminum plastic film to obtain the all-solid-state lithium battery, which is marked as 2-a.
To illustrate the synergy between the two electrolyte active materials in the present invention, li-free electrolyte active materials were separately assembled 20 Si 3 P 3 S 23 Cl, and no addition of Li 7 La 3 Zr 1.6 Ta 0.4 O 12 The all solid-state lithium batteries of (1) are respectively labeled as 2-b and 2-c.
Comparative example 2-1
(1) The cathode preparation procedure was the same as in example 2.
(2) Preparation process of the electrolyte membrane: mixing Li 7 La 3 Zr 1.6 Ta 0.4 O 12 And dispersing CMC and PTFE in acetonitrile according to a mass ratio of 92.5.5, stirring and mixing uniformly, evaporating the solvent to obtain a solid mixture, and repeatedly hot-pressing to form a film at 95 ℃ in a roller press with a heating function to ensure that the thickness of the rolled film is 60 micrometers, thus obtaining the electrolyte film.
(3) The procedure for preparing the anode was the same as in example 2, and an all solid-state lithium battery, designated 2-b, without addition of Li20Si3P3S23Cl was obtained.
Comparative examples 2 to 2
(1) The cathode preparation procedure was the same as in example 2.
(2) The preparation process of the electrolyte membrane comprises the following steps: mixing Li 20 Si 3 P 3 S 23 And dispersing Cl, CMC and PTFE in acetonitrile according to a mass ratio of 92.5 to 0.5, uniformly stirring and mixing, evaporating a solvent to obtain a solid mixture, and repeatedly performing hot pressing at 95 ℃ to form a film in a roller press with a heating function to ensure that the thickness of the rolled film is 60 micrometers, thus obtaining the electrolyte membrane.
(3) The procedure for preparing the anode was the same as in example 2, and an all solid-state lithium battery was obtained without addition of li7la3zr1.6ta0.4o12 and was labeled 2-c.
Comparative data of rate performance of three all-solid batteries obtained in example 2, comparative example 2-1 and comparative example 2-2 are shown in fig. 2, and it is obvious that the all-solid battery 2-a of the present invention has significantly higher discharge capacity and high rate discharge capacity. At the same time, it also shows that the two electrolyte materials can exert good synergistic effect.
Example 3
(1) The preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 Uniformly mixing the materials according to the mass ratio of 7:3 to obtain a mixture A3, and mixing the mixture A3 with Li 2 MnP 2 O 7 And PTFE and Super-P are placed in a high-shear mixer according to the mass ratio of 85.5.
(2) The preparation process of the electrolyte membrane comprises the following steps: mixing Li 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 Uniformly mixing the materials according to a mass ratio of 7:3 to obtain a mixture B3, dispersing the mixture B3, CMC and PTFE in acetonitrile according to a mass ratio of 80.
(3) The preparation process of the anode comprises the following steps: and (3) coating the In/Li alloy foil with the In/Li mass ratio of 90 to two sides of the copper foil, and rolling and shaping by using a roller press In an anhydrous and oxygen-free environment to obtain the anode of the all-solid-state lithium battery, wherein the shaping thickness is 15 mu m. After cathodes, electrolytes and anodes are alternately stacked and arranged in multiple layers, tabs are welded, and then the all solid-state lithium battery is packaged by an aluminum plastic film, the all solid-state lithium battery is fully charged in a constant-current-first-constant-voltage mode (current is 0.1C, cut-off voltage is 5V, and cut-off current is 0.02C), and then a stainless steel nail with the diameter of 2mm is adopted to carry out a needling experiment on the battery, and the change of the surface temperature of the prepared all solid-state battery along with time is shown in figure 3. It is apparent that the all-solid battery according to the present invention has excellent thermal stability.
The scope of the invention is not limited to the above embodiments, and various modifications and changes may be made by those skilled in the art, and any modifications, improvements and equivalents within the spirit and principle of the invention should be included in the scope of the invention.
Claims (10)
1. An all-solid-state lithium battery comprising a cathode, an electrolyte, and an anode, characterized in that:
the cathode comprises LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE, super-P and current-collecting carbon-coated aluminum foil;
the electrolyte comprises Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 CMC and PTFE;
the anode is an In/Li alloy foil and a current-collecting copper foil.
2. The all-solid-state lithium battery according to claim 1, characterized in that: liNi 0.5 Mn 1.5 O 4 The particle diameter of the material particles is 5-50 mu m, liFe 0.8 Mn 0.2 PO 4 The particle size of the material particles is 10-200nm.
3. The all-solid-state lithium battery according to claim 1 or 2, characterized in that: liNi in cathode 0.5 Mn 1.5 O 4 And LiFe 0.8 Mn 0.2 PO 4 The mass ratio of 3:7-7:3; in the cathode component except the carbon-coated aluminum foil of the current collector, li 2 MnP 2 O 7 The mass fractions of PTFE and Super-P are 0.5-10%.
4. The all-solid-state lithium battery according to claim 3, characterized in that: li in electrolyte 20 Si 3 P 3 S 23 Cl and Li 7 La 3 Zr 1.6 Ta 0.4 O 12 The mass ratio of 3:7-7:3; the mass fraction of CMC and PTFE in the electrolyte is 0.5-10%.
5. The all-solid-state lithium battery according to claim 4, characterized in that: the mass fraction of In the anode In/Li alloy foil is 70-95%.
6. The all-solid-state lithium battery according to claim 1 or 4, characterized in that: the auxiliary material comprises a tab and an aluminum-plastic film.
7. The method of manufacturing an all-solid-state lithium battery according to claim 6, comprising the steps of: firstly, respectively preparing a cathode, an electrolyte membrane and an anode, then alternately laminating the cathode, the electrolyte membrane and the anode for multiple layers, welding tabs, and then packaging by using an aluminum-plastic film to obtain the all-solid-state lithium battery;
wherein, the preparation process of the cathode comprises the following steps: reacting LiNi 0.5 Mn 1.5 O 4 、LiFe 0.8 Mn 0.2 PO 4 、Li 2 MnP 2 O 7 PTFE and Super-P are put in a stirrer according to the designed stoichiometry and are uniformly mixed, then an electrode film is formed by repeated hot pressing in a roller press with a heating function, and finally the electrode film is stuck on two sides of a current collector carbon-coated aluminum foil and is subjected to hot pressing and solidification to obtain the cathode of the all-solid-state battery;
the preparation process of the electrolyte membrane comprises the following steps: mixing Li 20 Si 3 P 3 S 23 Cl、Li 7 La 3 Zr 1.6 Ta 0.4 O 12 Dispersing CMC and PTFE in acetonitrile, stirring, mixing, evaporating solvent to obtain solid mixture, and hot pressing the solid mixture in a roller press with heating function to form film repeatedly to obtain the electrolytePlasma membranes.
8. The method of manufacturing an all-solid lithium battery according to claim 7, wherein the anode is manufactured by: and covering the two sides of the copper foil with the In/Li alloy foil, and rolling and shaping by using a rolling machine In a waterless and anaerobic environment to obtain the anode of the all-solid-state lithium battery.
9. The method for producing an all-solid lithium battery according to claim 7 or 8, characterized in that: and in the preparation process of the anode and the electrolyte membrane, the heating temperature of the heating roller press is 60-95 ℃.
10. The method for producing an all-solid-state lithium battery according to claim 9, characterized in that: the thickness of the cathode is 150-220 μm, the thickness of the electrolyte membrane is 60-120 μm, and the thickness of the anode is 15-30 μm.
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| CN115149091A (en) * | 2022-05-27 | 2022-10-04 | 湖州南木纳米科技有限公司 | Ta element doped LLZO composite solid electrolyte and low-temperature preparation method and application thereof |
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| JP2014060084A (en) * | 2012-09-19 | 2014-04-03 | Ohara Inc | All solid-state lithium ion secondary battery |
| CN106165155A (en) * | 2014-02-11 | 2016-11-23 | 康宁股份有限公司 | Comprise the lithium ion battery of stable lithium composite particles |
| CN109980273A (en) * | 2017-12-27 | 2019-07-05 | 现代自动车株式会社 | All-solid-state battery group |
| JP2021051825A (en) * | 2019-09-20 | 2021-04-01 | Fdk株式会社 | All-solid battery, positive electrode and production method of all-solid battery |
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