CN110429281A - A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte - Google Patents

A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte Download PDF

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CN110429281A
CN110429281A CN201910708636.4A CN201910708636A CN110429281A CN 110429281 A CN110429281 A CN 110429281A CN 201910708636 A CN201910708636 A CN 201910708636A CN 110429281 A CN110429281 A CN 110429281A
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solid electrolyte
sulfide solid
state battery
energy density
sulfide
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许晓雄
黄晓
吴林斌
张秩华
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Zhejiang Feng Li Amperex Technology Ltd
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Zhejiang Feng Li Amperex Technology Ltd
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    • 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
    • H01M10/0468—Compression means for stacks of electrodes and separators
    • 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
    • H01M10/60—Heating or cooling; Temperature control
    • H01M10/61—Types of temperature control
    • H01M10/615—Heating or keeping warm
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 kind of high-energy density all-solid-state battery based on sulfide solid electrolyte; it is related to all-solid-state battery field, including cathode, sulfide solid electrolyte and anode, the negative electrode material of the cathode is lithium metal; the metallic lithium surface covers matcoveredn, and the protective layer is Li3N, a kind of in LiF and LiI.By using above-mentioned technical proposal, by Li3N, LiF and LiI can effectively completely cut off contact of the lithium metal with sulfide solid electrolyte as protective layer, generate stable material so as to avoid reacting between the two, and influence the normal use of all-solid-state battery.In addition, due to Li3N, the intermiscibility between LiF and LiI and sulfide solid electrolyte will be got well compared between elemental metals lithium and sulfide solid electrolyte, be conducive to reduce interface impedance in this way, be transmitted between sulfide solid electrolyte and lithium metal to improve ion.

Description

A kind of high-energy density all-solid-state battery based on sulfide solid electrolyte
Technical field
The present invention relates to solid state battery field, in particular to a kind of high-energy density based on sulfide solid electrolyte is complete Solid state battery.
Background technique
With the continuous development of all-solid-state battery industry, lithium metal and sulfide both materials have received industry It pays special attention to, wherein lithium metal is used as negative electrode material or is used sulfide as solid electrolyte, can improve The electrical property of all-solid-state battery.
For this purpose, the manufacturing enterprise of part all-solid-state battery consider by lithium metal and sulfide carry out jointly using, with into The performance of one step raising all-solid-state battery.But at the same time due to the relationship of lithium metal and sulfide itself chemical property, The two directly contacts and is easy for reacting, to will lead to contact in lithium metal Surface Creation barrier metal lithium and sulfide Stable material will make battery over time so that the ion transmission efficiency between lithium metal and sulfide will be reduced Internal resistance rise, and then all-solid-state battery will be made to fail.Such as with Li10GeP2S12For, after being contacted with lithium metal, Ge4 +、P5+It is reduced into Ge metal and Li3P, reaction equation are as follows:
Li10GeP2S12+20Li++20e−→Ge0+2Li2P+12Li2S
Product Ge has electronic conductance, can further transmit electronics, and the LGPS for being supplied to electrolyte depths is decomposed, until electrolyte Layer all decomposes.Further, product Li3P、Li2Ion, the electronic conductivity of S is very low, to completely cut off lithium anode and electricity The contact between matter is solved, and then increases the internal resistance of battery.
Therefore, this is also there is technical issues that in the industry, it would be highly desirable to be solved.
Summary of the invention
The object of the present invention is to provide a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte, effectively Ground avoids the normal use for reacting and influencing all-solid-state battery between lithium metal and sulfide solid electrolyte.
Foregoing invention purpose of the invention has the technical scheme that a kind of based on sulfide solid electricity Solve the high-energy density all-solid-state battery of matter, including cathode sulfide solid electrolyte and anode, the negative electrode material of the cathode For lithium metal, the metallic lithium surface covers matcoveredn, and the protective layer is Li3N, a kind of in LiF and LiI.
By using above-mentioned technical proposal, by Li3N, LiF and LiI is as protective layer, can effectively completely cut off lithium metal and The contact of sulfide solid electrolyte generates stable material so as to avoid reacting between the two, and influences all solid state electricity The normal use in pond.
In addition, due to Li3N, the intermiscibility between LiF and LiI and sulfide solid electrolyte is compared to elemental metals lithium It to be got well between sulfide solid electrolyte, be conducive to reduce interface impedance in this way, to improve ion in sulfide solid It is transmitted between electrolyte and lithium metal.
Preferably, the protective layer with a thickness of 20nm~10um.
By using above-mentioned technical proposal, on the one hand can guarantee in this way protective layer in the adhesive force of metallic lithium surface, from And ensure that the protection to lithium metal, on the other hand it can also guarantee voltage of the lithium metal as negative electrode material, thus effectively It ensure that the high-energy density state of battery.
Preferably, the preparation method of protective layer is that lithium metal is placed in N coated on collector later2、F2、NO2、HF And I22min~4h is handled in any one atmosphere of steam, can form corresponding protective layer in metallic lithium surface.
Preferably, N2、F2、NO2, HF or I2The flow velocity of steam is 0.5~3m3/ h, temperature are 20 DEG C.
By using above-mentioned technical proposal, be conducive to improve Li in this way3N, the effect that LiF and LiI is formed in metallic lithium surface Rate.
Preferably, the anode includes one of nickelic ternary material or rich lithium material.
By using above-mentioned technical proposal, anode uses the nickelic ternary material of high capacity, by means of the high capacity of lithium metal, Cathode dosage can be reduced, realizes the specific capacity of high solid state battery.
By using above-mentioned technical proposal, lithium additive is mended by adding in anode, can be avoided filled for the first time in this way In discharge process, cathode consumes excessive lithium and impacts to the performance of battery the application.
Preferably, the sulfide solid electrolyte is Li10GeP2S12Class Li9.54Si1.74P1.44S11.7Cl0.3、Thio- LISICON class Li3.25Ge0.25P0.75S4、Li2S-P2S5Class Li3PS4 Li7P3S11, argyrodite class Li6PS5Cl、 Li5.5PS4.5Cl1.5、Li2S-P2S5- LiX(X=Br I) class Li7P2S8Br0.5I0.5And Li2S-P2S5-X2(X=Br, I) class 70Li2S-20P2S5-5Br2-5I2One or more of mixture.
By using above-mentioned technical proposal, using selected sulfide solid electrolyte, can effectively guarantee so complete Solid state battery has higher energy density always.
Preferably, it after sulfide solid electrolyte being mixed with toluene, is coated on positive plate and negative electrode tab, it later will just Negative electrode tab in 60 DEG C ~ 80 DEG C dryings to it is thick when, the two is fit together.
By using above-mentioned technical proposal, enable intermiscibility between protective layer and sulfide solid electrolyte into one Step improves, to weaken the interface impedance between cathode and sulfide solid electrolyte, and then ensure that cathode and sulfide The conductivity of electrons/ions between solid electrolyte.
Preferably, that positive and negative anodes after fitting are placed in the following roll-in side of 80 DEG C ~ 200 DEG C conditions is dry, and the duration is 60 ~ 200s。
It is dry on the following roll-in side of 80 DEG C ~ 200 DEG C conditions by using above-mentioned technical proposal, it can make to be coated in this way Vulcanized solid electrolyte on positive plate and negative electrode tab can preferably carry out it is compatible, thus further weaken anode, vulcanization Interface impedance between object solid electrolyte and cathode.
In conclusion advantageous effects of the invention are as follows:
1, protective layer is formed in metallic lithium surface, can be directly connect between barrier metal lithium and sulfide solid electrolyte in this way Touching generates stable material so as to avoid reaction between lithium metal and sulfide solid electrolyte, and influences all-solid-state battery Normal use；
2, the mode that battery core is carried out to high pressure or heating can effectively weaken cathode and sulfide solid electricity
The interface impedance between matter is solved, so as to effectively guarantee the properties of all-solid-state battery.
Detailed description of the invention
Fig. 1 is a kind of preparation technology flow chart of high-energy density all-solid-state battery based on sulfide solid electrolyte.
Specific embodiment
Below in conjunction with attached drawing 1, invention is further described in detail.
Embodiment one,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in N22h in atmosphere, and keep N2Flow velocity be 3 m3/ h, temperature 20 DEG C, 5umLi is formed in metallic lithium surface to obtain3The negative electrode tab of N protective layer；
Step 3: by sulfide solid electrolyte Li9.54Si1.74P1.44S11.7Cl0.3, NCA positive electrode, conductive black and poly- inclined Vinyl fluoride is incorporated in toluene for 30:65:3:2 with mass ratio and is sufficiently mixed, and the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li9.54Si1.74P1.44S11.7Cl0.3Powder is mixed with toluene, is prepared into the electrolysis chylema that solid content is 40% Material, later using thermal spraying even application on positive plate and negative electrode tab；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and 100 DEG C ~ 120 The following roll-in side of DEG C condition is dry, duration 200s, so that it is guaranteed that positive and negative anodes with sulfide electrolyte layer is intact is bonded, drop The low internal resistance of cell, and then obtain battery core；
Step 7: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Embodiment two,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in F21h in atmosphere, and keep F2Flow velocity be 1m3/ h, temperature 20 DEG C, the negative electrode tab of 5umLiF protective layer is formed in metallic lithium surface to obtain；
Step 3: by sulfide solid electrolyte Li3.25Ge0.25P0.75S4, NCA positive electrode, conductive black and Kynoar It is incorporated in toluene and is sufficiently mixed for 30:65:3:2 with mass ratio, the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li3.25Ge0.25P0.75S4Powder is mixed with toluene, is prepared into the electrolyte slurry that solid content is 40%, later Even application is on positive plate and negative electrode tab by the way of thermal spraying；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and in 80 ~ 100 DEG C of items The following roll-in side of part is dry, is continuously 100s, it is ensured that positive and negative anodes with sulfide electrolyte layer is intact is bonded, the reduction internal resistance of cell, And then obtain battery core；
Step 7: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Embodiment three,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in I21h in steam, and keep I2The flow velocity of steam is 1m3/ s, temperature are 20 DEG C, the negative electrode tab of 5umLiI protective layer is formed in metallic lithium surface to obtain；
Step 3: by sulfide solid electrolyte Li6PS5Cl, NCA positive electrode, conductive black and Kynoar are with quality It is sufficiently mixed than being incorporated in toluene for 30:65:3:2, the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li6PS5Cl powder is uniformly mixed with toluene, is prepared into the electrolyte slurry that solid content is 40%, is adopted later With the mode even application of thermal spraying on positive plate and negative electrode tab；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and in 200 DEG C of conditions Following roll-in side is dry, continues 60s, it is ensured that positive and negative anodes with sulfide electrolyte layer is intact is bonded, reduce the internal resistance of cell, and then obtain To battery core；
Step 6: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Example IV,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in 4h in HF, and keeping the flow velocity of HF is 1m3/ h, temperature are 20 DEG C, from And it obtains and is formed with the negative electrode tab of 5umLiF protective layer in metallic lithium surface；
Step 3: by Li7P2S8Br0.5I0.5, NCA, conductive black and Kynoar be incorporated in mass ratio for 30:65:3:2 It is sufficiently mixed in toluene, the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li7P2S8Br0.5I0.5It is mixed with toluene, is prepared into the electrolyte slurry that solid content is 40%, adopts later With the mode even application of thermal spraying on positive plate and negative electrode tab；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and at 100-120 DEG C The following roll-in side of condition is dry, is continuously 200s, it is ensured that positive and negative anodes with sulfide electrolyte layer is intact is bonded, in reduction battery Resistance, and then obtain battery core；
Step 7: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Embodiment five,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in NO2Middle 0.5h, and keep NO2Flow velocity be 1m3/ h, temperature 20 DEG C, 2umLi is formed in metallic lithium surface to obtain3N and Li2The negative electrode tab of the mixed protection layer of O；
Step 3: by Li7P3S11, NCA positive electrode, conductive black and Kynoar with mass ratio be that 30:65:3:2 is added It is sufficiently mixed in toluene, the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li7P3S11It is mixed with toluene, is prepared into the electrolyte slurry that solid content is 40%, uses thermal jet later The mode even application of painting is on positive plate and negative electrode tab；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and 100 DEG C ~ 120 The following roll-in side of DEG C condition is dry, duration 80s, it is ensured that positive and negative anodes with sulfide electrolyte layer is intact is bonded, reduce electric Pond internal resistance, and then obtain battery core；
Step 7: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Embodiment six,
A kind of preparation method of the high-energy density all-solid-state battery based on sulfide solid electrolyte, includes the following steps:
Step 1: by lithium metal coated on clean copper foil；
Step 2: the copper foil with lithium metal is placed in N22h in atmosphere, and keep N2Flow velocity be 3 m3/ h, temperature 20 DEG C, 5umLi is formed in metallic lithium surface to obtain3The negative electrode tab of N protective layer；
Step 3: by sulfide solid electrolyte Li2S-P2S5-Br2-I2, NCA positive electrode, conductive black and Kynoar It is incorporated in toluene and is sufficiently mixed for 30:65:3:2 with mass ratio, the anode sizing agent that solid content is 20% ~ 80% is made；
Step 4: by anode sizing agent even application on aluminium foil, and applied thickness is 25 μm, and is 110 DEG C ~ 150 DEG C in temperature Under be dried, later again after roll-in and cutting, be made positive plate；
Step 5: by Li2S-P2S5-Br2-I2Powder is mixed with toluene, is prepared into the electrolyte slurry that solid content is 40%, later Using thermal spraying even application on positive plate and negative electrode tab；
Step 6: by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to thick, after being later bonded positive and negative anodes and 100 DEG C ~ 120 The following roll-in side of DEG C condition is dry, duration 200s, so that it is guaranteed that positive and negative anodes with sulfide electrolyte layer is intact is bonded, drop The low internal resistance of cell, and then obtain battery core；
Step 7: installing tab in battery core and coating with aluminum plastic film, battery outer box is installed, obtains final all solid lithium electricity Pond.
Comparative example one,
Difference with embodiment one is only that the lithium metal of negative electrode tab is not in N2It is handled under atmosphere.
Comparative example two,
Difference with embodiment two is only that the lithium metal of negative electrode tab is not in F2It is handled under atmosphere.
Comparative example three,
Difference with embodiment three is only that the lithium metal of negative electrode tab is not in I2It is handled under steam atmosphere.
Comparative example four,
Difference with example IV is only that the lithium metal of negative electrode tab is not handled under HF atmosphere.
Comparative example five,
Difference with embodiment five is only that the lithium metal of negative electrode tab is not in NO2It is handled under atmosphere.
Comparative example six,
Difference with embodiment six is only that the lithium metal of negative electrode tab is not in N2It is handled under atmosphere.
To embodiment one to embodiment six and comparative example one to comparative example six, tested as follows:
Be 0.05C(20h with the theoretical capacity relative to battery) electric current carry out constant current charge-discharge.Blanking voltage be 3.0V ~ 4.2V.Then, with 0.5C circulation 99 times.Record coulombic efficiency for the first time, for the first time with discharge capacity when the 100th circulation (with Positive active material Mass Calculation).As a result as shown in Table 1.
One embodiment one of table is to embodiment six and comparative example one to the test result of comparative example six
Coulombic efficiency for the first time Discharge capacity (mAh/g) for the first time Discharge capacity (mAh/g) after 100 circulations Capacity retention ratio
Embodiment 1 83.7 160.3 144.0 89.8%
Embodiment 2 78.9 149.9 135.2 90.2%
Embodiment 3 92.6 180.0 169.0 93.9%
Embodiment 4 81.5 155.2 108.7 70.0%
Embodiment 5 85.9 165.1 115.7 70.1%
Embodiment 6 92.8 184.8 173.8 94.0%
Comparative example 1 50.7 95.9 57.8 60.2%
Comparative example 2 47.9 89.5 54.0 60.3%
Comparative example 3 74.2 144.0 93.2 64.7%
Comparative example 4 79.6 149.6 89.5 59.9%
Comparative example 5 73.3 140.5 84.4 60.1%
Comparative example 6 85.3 169.9 153.0 90.1%
Analysis of conclusion: after being compared by embodiment one to embodiment five and comparative example one to comparative example five, it can be seen that gold Belong to lithium and passes through N2、F2、I2Steam, HF or NO2After processing, obtained all-solid-state battery 100 capacity guarantor still with higher after enclosing Holdup.
Wherein, Li6PS5Cl and Li2S-P2S5-Br2-I2Two electrolytelike performances are relative to other kind of based solid electrolyte More preferably.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the art Member can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at this All by the protection of Patent Law in the scope of the claims of invention.

Claims (8)

1. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte, including the electrolysis of cathode, sulfide solid Matter and anode, the negative electrode material of the cathode are lithium metal, it is characterised in that: the surface of the lithium metal covers matcoveredn, The protective layer is Li3N, a kind of in LiF and LiI.
2. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 1, special Sign is: the protective layer with a thickness of 20nm~10um.
3. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 1, special Sign is: the preparation method of protective layer is that lithium metal is placed in N coated on collector later2、F2、NO2, HF and I2Steam Any one atmosphere in handle 2min~4h, corresponding protective layer can be formed in metallic lithium surface.
4. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 3, special Sign is: N2、F2、NO2, HF or I2The flow velocity of steam is 3~5m/s, and temperature is 20~77 DEG C.
5. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 1, special Sign is: the anode includes one of nickelic ternary material or rich lithium material.
6. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 1, special Sign is: the sulfide solid electrolyte is Li10GeP2S12Class Li9.54Si1.74P1.44S11.7Cl0.3, Thio-LISICON class Li3.25Ge0.25P0.75S4、Li2S-P2S5Class Li3PS4And Li7P3S11, argyrodite class Li6PS5Cl、Li5.5PS4.5Cl1.5、Li2S- P2S5- LiX(X=Br I) class Li7P2S8Br0.5I0.5And Li2S-P2S5-X2(X=Br, I) class 70Li2S-20P2S5-5Br2-5I2In One or more kinds of mixtures.
7. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 1, special Sign is: after sulfide solid electrolyte is mixed with toluene, coated on positive plate and negative electrode tab, later by positive/negative plate in 60 DEG C ~ 80 DEG C dryings to it is thick when, the two is fit together.
8. a kind of high-energy density all-solid-state battery based on sulfide solid electrolyte according to claim 7, special Sign is: positive and negative anodes after fitting being placed in the following roll-in side drying of 80 DEG C ~ 200 DEG C conditions, the duration is 60 ~ 200s.
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