CN108145165B - The method that 3D printing prepares metal lithium bands - Google Patents

The method that 3D printing prepares metal lithium bands Download PDF

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Publication number
CN108145165B
CN108145165B CN201711328593.4A CN201711328593A CN108145165B CN 108145165 B CN108145165 B CN 108145165B CN 201711328593 A CN201711328593 A CN 201711328593A CN 108145165 B CN108145165 B CN 108145165B
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printing
lithium
thickness
layer
gas
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CN108145165A (en
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曹乃珍
邹崴
刘强
詹彬鑫
李娇
徐川
高洁
何霞
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Tianqi Lithium Industry Co Ltd
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Tianqi Lithium Industry Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/115—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces by spraying molten metal, i.e. spray sintering, spray casting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y50/00—Data acquisition or data processing for additive manufacturing
    • B33Y50/02—Data acquisition or data processing for additive manufacturing for controlling or regulating additive manufacturing processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
    • B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
    • B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
    • B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method

Abstract

The present invention relates to lithium metal technical fields, disclose a kind of preparation method of metal lithium bands.The 3D printing prepares the method for metal lithium bands on the basis of existing 3D printing technique, it is targetedly improved for the characteristic of lithium metal, using the fixed point layer-by-layer printing type of territory element, in the case where lithium metal ink head and substrate are opposing stationary, realize the quick layer-by-layer printing of territory element, it is not only advantageous to the control of print thickness, and the partial oxidation reaction that lithium metal may occur in print procedure can be better protected from, to improve the quality of lithium band, this method is especially suitable for lithium layer with a thickness of the preparation of 3~100 μm of metal lithium bands.

Description

The method that 3D printing prepares metal lithium bands
Technical field
The present invention relates to lithium metal technical field, especially a kind of preparation method of metal lithium bands.
Background technique
The fast development of electric car proposes new higher requirement to lithium electrical power densities.Lithium metal has very high Specific energy density (3860mAh/g), be the optimal selection of the following high energy battery negative electrode material, for this purpose, preparation band protective film Metal lithium bands (especially ultrathin metal lithium strip) become current research hotspot.
Generally use machinery at present and prolong platen press and prepare lithium strip, but prolong platen press there are the following problems: 20 μm of preparation with Lower ultra-thin lithium film is difficult to realize；Disposable preparation complex lithium band is difficult；Prolong that pressure lithium band yield rate is low, leftover pieces are more, lithium raw material are unrestrained Fei great；Prolong platen press lithium band mechanical precision requirement height, equipment investment is big.It is currently many about the research of this respect, but be difficult to take Obtain real-time progress, it is difficult to be produced in batches.As CN201510274673.0 patent is lubricated processing to substrate first, then Using complex composite roll-in, stripping technology, single side self-supporting, 30 μm of thickness of lithium film can be finally prepared. CN200920251219.3 patent prepares the lithium foil with passivation layer using mechanical calendering technology, easily draws in process of production Stretch the deformation even exception of fracture；CN201610393493.9 patent proposes a kind of temperature control calendering lithium band device of complexity, with Ensure to prolong consistency of the pressure lithium film in terms of thickness and hardness.Prolong the problems of platen press in view of machinery, and has developed as heavy The preparation method of a variety of lithium bands of area method, but because many factors are not widely used yet so far.
3D printing technique is otherwise known as increases material manufacturing technology.The core of the technology is 3D printer, printer and computer phase Even, it is controlled by computer, is worked by the procedural model write in advance.At work, printer utilizes light according to program instruction The technologies such as solidification and paper layer are folded, " printed material " (generally solid filament, powder or the liquid) in printer is superimposed from level to level Get up, finally obtained target is in kind.Instantly 3D printing technique is more popular research and application industry, but is not had also so far People is applied to the preparation of metal lithium bands.One kind, which is disclosed, application No. is the patent document of CN201510554429.X passes through 3D Printing production TiO2The preparation method of multifunctional membrane, by passing through after mixing organic titanium powder and nano titanium dioxide powder 3D printing film forming, is then made TiO by sintering2Multifunctional membrane.It is practical not become hot technology also early in 3D printing technique 2001, in the way of traditional inkjet printing prepared by metallic film with regard to someone, the technology be disclosed in application No. is In the patent document of CN01128004.2, specific method is to generate the compound of metal using thermal decomposition as raw material and solvent And additive is made into ink-jet ink, is deposited on substrate using typical inkjet printing technique, then in 200~600 DEG C of temperature Ink is set to be thermally decomposed into metallic film under degree.It is that can only prepare Fe, Au, Cu, Ag, Pb, Pt that such mode, which has a great limitation, Etc. torpescence metallic film, and be not suitable for this kind of active metal of lithium metal.
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of methods that 3D printing prepares metal lithium bands, not only can be with Ultrathin metal lithium strip is prepared, and thickness control is accurate, lithium layer quality is high.
The method that 3D printing disclosed by the invention prepares metal lithium bands, includes the following steps:
A, lithium tape thickness to be prepared is inputted in 3D printer；
B, substrate is divided into several territory elements to print, positions initiation region unit, in a protected environment, metal Lithium ink head is directed at initiation region unit and carries out successively superposition printing, and lithium metal ink head and substrate is made to keep opposite in print procedure Static, lithium layer thickness completes the printing of initiation region unit after being superimposed to preset thickness；
C, mobile black head or substrate make black head alignment subsequent region unit, under black head and the opposing stationary situation of substrate into The printing of row subsequent region unit obtains metal lithium bands until the printing of all areas unit is completed.
Preferably, protective layer ink head is set on 3D printer；In b step and step c, in the lithium layer of a territory element After the completion of printing, protective layer is printed in lithium layer using protective layer ink head.
Preferably, the 3D printer is provided with gas forging machine structure, and the gas forging machine structure includes the gentle forging of pressure-driven connecting rod Idler wheel, the gas forging idler wheel are set to pressure-driven interlinking lever end, and the gas forging roller surface is evenly arranged with gas forging hole, described Gas forging hole is connected with inert gas delivery pipe；
In b step and step c, after the printing for completing territory element, lithium band is forged and pressed using gas forging machine structure, gas forging Idler wheel is in contact with the protective layer of territory element and micro-positive pressure is kept to be rolled, and is passed through constant temperature inertia from inert gas delivery pipe Gas, inert gas forge hole by the gas that gas forges roller surface and carry out gas forging and stamping to territory element.
Preferably, the rolling pressure of the gas forging idler wheel is 10~100KPa, and the pressure of the gas forging and stamping is 1~15MPa.
Preferably, the lithium layer print thickness that single layer is preset in 3D printer is calculated according to the lithium tape thickness of input and is beaten The number of plies is printed, print thickness is controlled by the number of plies of control printing lithium layer in b step and step c.
Preferably, in b step and step c, by the thickness detection apparatus lithium layer cumulative thickness that has printed of monitoring and real When feed back to 3D printer, 3D printer adjusts the remaining printing number of plies according to monitoring data and realizes thickness control.
Preferably, in b step and step c, by the thickness detection apparatus lithium layer cumulative thickness that has printed of monitoring and real When feed back to 3D printer, 3D printer adjusts the printing number of plies according to monitoring data and single layer print thickness realizes thickness control.
Preferably, in the layer-by-layer superposition printing of the territory element, the territory element is rectangle, the area of territory element For 0.005~0.1mm2, single layer print thickness is 0.5~1.0 μm.
Preferably, the lithium layer of prepared metal lithium bands is with a thickness of 3~100 μm.
Preferably, lithium metal temperature is 300~1000 DEG C in the lithium metal ink head.
Preferably, in the protective layer ink head raw material be organic film class, salts or solid electrolyte class, it is described organic Film class is fluorine dragon, polyethylene, polypropylene, polyurethane or polytetrafluoroethylene (PTFE), and the salts are Li2CO3Or Li3PO4, described Solid electrolyte class is LPON, NASICON or sulfide.
Preferably, the substrate be copper foil, aluminium foil, rustless steel foil, aluminum plastic film, nylon membrane, polyethylene film, polypropylene screen, Polychloroethylene film, polyester film or graphite cathode band.
The beneficial effects of the present invention are: the 3D printing prepares the method for metal lithium bands on the basis of existing 3D printing technique On, it is targetedly improved for the characteristic of lithium metal, the layer-by-layer printing type of territory element is used, in lithium metal ink head With substrate it is opposing stationary in the case where, realize the quick layer-by-layer printing of territory element, be not only advantageous to the control of print thickness, and And it can be better protected from the partial oxidation reaction that lithium metal may occur in print procedure, so that the quality of lithium band is improved, This method is especially suitable for lithium layer with a thickness of the preparation of 3~100 μm of metal lithium bands.
Detailed description of the invention
Fig. 1 is the simplified schematic diagram of 3D printer of the invention；
Fig. 2 is the simplified schematic diagram of gas forging machine structure of the invention.
Appended drawing reference: 3D printer 1, lithium metal ink head 2, gas forging machine structure 3, drive link 31, gas forge idler wheel 32, indifferent gas Body delivery pipe 33, flow electric valve 34, protective layer ink head 4, curing mechanism 5, support platform 6, substrate 7, lithium layer 8, protective layer 9, Print shield 10.
Specific embodiment
The present invention is further described below.
The method that 3D printing disclosed by the invention prepares metal lithium bands, includes the following steps:
A, lithium tape thickness to be prepared is inputted in 3D printer 1；
B, substrate 7 is divided into several territory elements to print, the substrate 7 can use copper foil, aluminium foil, rustless steel Foil, aluminum plastic film, nylon membrane, polyethylene film, polypropylene screen, polychloroethylene film, polyester film or graphite cathode band etc., positioning starting Territory element, in a protected environment, lithium metal ink head 2 are directed at initiation region unit and carry out successively superposition printing, in print procedure In so that lithium metal ink head 2 is kept opposing stationary with substrate 7,8 thickness of lithium layer, which is superimposed to after preset thickness, completes initiation region unit Printing；
C, mobile black head or substrate 7 make black head alignment subsequent region unit, under black head and the opposing stationary situation of substrate 7 The printing of subsequent region unit is carried out, until the printing of all areas unit is completed, obtains metal lithium bands.
For the determination up to standard of thickness, various ways, such as setting thickness detection apparatus, real-time monitoring can be used Print thickness and Real-time Feedback are to 3D printer 1, and 3D printer 1 according to monitoring data adjusts the printing number of plies and single layer prints Lithium metal amount stops the printing in the region after thickness detection apparatus measurement thickness is up to standard, and the advantage of such mode is can be with By repeatedly adjusting control, the precision of thickness control is improved.The consistency that for another example can accurately control every layer of print thickness, passes through The lithium tape thickness to be prepared of input is divided by every layer of print thickness, so that it may calculate the number of plies of printing, then be beaten by control The print number of plies realizes the control of print thickness, such control mode it is more simple, have higher efficiency.On the basis of, also It by thickness detection apparatus can monitor 8 cumulative thickness of lithium layer that has printed and Real-time Feedback is to 3D printer 1,3D printer 1 The remaining printing number of plies is adjusted according to monitoring data, to improve printing precision.Wherein, thickness detection apparatus generallys use high-precision Non contact thickness gaging device, for example, X-ray ga(u)ging degree instrument, spectrum on line calibrator, quartz crystal oscillation calibrator etc..
In general, successively printing type is more advantageous to the control of print thickness relative to single layer printing, such as using above The first thickness control mode, multiple thickness control and adjustment may be implemented in print procedure, allow territory element print Overall thickness control is more accurate.It is practical that layer-by-layer printing type has also been mostly used in existing 3D printing technique, still, the present invention Different from the round-trip printing type of black head in general 3D printing technique, but uses lithium metal ink head 2 and keep opposite with substrate 7 The layer-by-layer printing type of static fixed point, such mode due in print procedure lithium metal ink head 2 and substrate 7 may be at it is static State there is no need to regulate and control relative moving speed and amount out of ink and frequency out of ink, therefore has high beat in territory element Frequency is printed, the thinner of every layer of printing can be made, it, can especially when using previously described second of thickness control mode To accomplish higher control precision；And static fixed point is successively printed and can also be avoided in round-trip print procedure because black head is mobile The matching problem of speed and flow out of ink and caused by thickness error.Although in addition, being printed upon the protection such as vacuum or inert gas Under environment, but it is practical due to apparatus factor, it is only capable of accomplishing opposite insulation blocking, according to traditional round-trip impression block of multilayer The defects of formula, in multilayer two-way process, partial oxidation reaction may occur for the film layer newly printed, generate oxide, influences Lithium layer quality；And the present invention is used and is successively printed on the same area unit, between highly shortened between layers Every the time, lithium probability is greatly reduced, finally improves lithium layer quality.For convenience of the rank between adjacent area unit It connects, in the layer-by-layer superposition printing of the territory element, the territory element is rectangle, and the area requirements ink head of territory element is not In the case where movement, it can be accomplished effectively to cover, therefore the area of territory element is usually 0.005~0.1mm2, single Layer print thickness directly affects the accuracy of thickness control, and usual single layer print thickness is thinner, is more easy to control print thickness, comprehensive The precision of existing black head apparatus is closed, single layer print thickness is 0.5~1.0 μm.
Because lithium metal, which is once in contact with air, will occur oxidation reaction, in order to protect the metal lithium bands printed, Protective layer ink head 4 is set on 3D printer 1；In b step and step c, after the completion of the lithium layer 8 of a territory element prints, Protective layer 9 is printed in lithium layer 8 using protective layer ink head 4.It is similar, for the ease of controlling the thickness of protective layer 9, in a step, Input 9 thickness of protective layer；In b step and step c, protective layer 9 is using successively superposition printing, until reaching preset thickness, completes The printing of territory element.The thickness control mode of protective layer 9 is consistent with the control mode of lithium layer 8.It is former in the protective layer ink head 4 Material be organic film class, salts or solid electrolyte class, the organic film class be fluorine dragon, polyethylene, polypropylene, polyurethane or Polytetrafluoroethylene (PTFE) etc., the salts are Li2CO3Or Li3PO4Deng, the solid electrolyte class be LPON, NASICON or Sulfide etc..Simultaneously in order to accelerate the solidification printed, the 3D printing is additionally provided with curing mechanism 5, opens in the whole process of printing Curing mechanism 5 promotes quickly being set in substrate 7 for printable layer.Laser curing, injection stream solidification etc. can be used in curing mechanism 5 A variety of curing modes.
Since liquid lithium-surface tension is larger, for the uniformity for improving printing, lithium metal is printed using super fusing point, is surpassed Melting temperature printing refers to that print temperature is apparently higher than lithium liquid melting temperature and is lower than evaporating temperature, in practical operation, the gold Belonging to lithium metal temperature in lithium ink head 2 is 300~1000 DEG C.
After the completion of a territory element, printed at once in adjacent territory element, lithium metal fusing point is very low, individually The print time of territory element is very short, and the lithium metal temperature difference of adjacent area unit is smaller, can accomplish between territory element very well Ground linking.And in order to further enhance the linking of adjacent area unit, and the uniformity of lithium layer 8 is improved, the 3D printer 1 is set It is equipped with gas forging machine structure 3, the gas forging machine structure 3 includes drive link 31, gas forging idler wheel 32 and inert gas delivery pipe 33, the gas Forging idler wheel 32 is connected in drive link 31, if being provided with dry gas forging hole on gas forging idler wheel 32, the inert gas conveying Pipe 33 is connected with gas forging hole；
In b step and step c, after the printing for completing territory element, lithium band is forged and pressed using gas forging machine structure 3, gas Forging idler wheel 32 is in contact with the protective layer 9 of territory element and micro-positive pressure is kept to be rolled, and is passed through from inert gas delivery pipe 33 Constant temperature inert gas, inert gas forge hole by the gas that gas forges 32 surface of idler wheel and carry out gas forging and stamping to territory element, and gas forges idler wheel The pressure that 32 rolling pressure is forged and pressed relative to gas is much smaller, and the rolling pressure of usually gas forging idler wheel 32 is 10~ The pressure of 100KPa, the gas forging and stamping are 1~15MPa.The gas that gas forging and stamping herein are different from tradition forging forges mode, The air-flow constantly, stable used in forging and stamping applies pressure to lithium band, to improve the uniformity of lithium band, and enhances region The linking of unit.It should be noted that idler wheel 32 directly rolls is the outermost protective layer 9 of lithium band for gas forging, without with lithium metal Directly contact.In the lithium band printing of unprotect layer 9, gas forging idler wheel 32 is not in contact equally with lithium band, and merely with stable Inert gas flow carries out gas forging to it.
The method for further preparing metal lithium bands to 3D printing disclosed by the invention in the form of embodiment below is said It is bright.
Embodiment 1
The lithium layer of 10 μ m-thicks is printed in the PE film strips with a thickness of 10 μm.
Set 0.8 μm of single layer print thickness of lithium metal ink head 2, printing covering on 3D printer 1 in advance before printing 0.1mm2Square area.
When printing, printing raw material is added in 3D printer 1, lithium metal is heated to 350 DEG C, is inputted in 3D printer 1 After 8 thickness of lithium layer to be prepared, can calculate the number of plies to be printed on each territory element automatically is 13.Using with a thickness of 10 μm of PE film is placed in support platform 6 as substrate 7, and support platform 6 has smooth and adsorption function to substrate 7, Printing environment applying argon gas is protected.Start to print after the completion of preparation, firstly, positioning initiation region unit, lithium metal Black head 2 is directed at initiation region unit and carries out successively superposition printing, and lithium metal ink head 2 is made to keep phase with substrate 7 in print procedure To static, after printing the number of plies and reaching calculation amount, mobile lithium metal ink head 2 to adjacent subsequent region unit is printed, directly It prints and completes to all areas unit, obtain metal lithium bands.
Detection is measured to the metal lithium bands of preparation, surfacing is uniform, and metallic lithium layer 8 is with a thickness of 11.1 μm.
Embodiment 2
The lithium layer of 20 μ m-thicks, and the protective layer 9 of additional 5 μ m-thicks are printed on the copper foil tape with a thickness of 10 μm.
Using the 3D printer 1 with lithium metal ink head 2, protective layer ink head 4 and gas forging machine structure 3, before printing in advance 0.8 μm of single layer print thickness of lithium metal ink head 2, printing covering 0.1mm are set on 3D printer 12Square area, protect Sheath ink head 4 prints overlay area and lithium metal ink head 2 is completely the same.
When printing, printing raw material is added in 3D printer 1, selects polyethylene as 9 raw material of protective layer, heats lithium metal To 500 DEG C, after 9 thickness of lithium layer 8 to be prepared and protective layer is inputted in 3D printer 1, each region can be calculated automatically 8 number of plies of metallic lithium layer to be printed on unit is 27, and 9 number of plies of protective layer is 7.Using the copper foil tape with a thickness of 10 μm as base Bottom 7 is placed in support platform 6, is protected to printing environment applying argon gas.Start to print after the completion of preparation, it is first First, initiation region unit is positioned, lithium metal ink head 2 is directed at initiation region unit and carries out successively superposition printing, in print procedure Keep lithium metal ink head 2 and substrate 7 to be in stationary state, after printing the number of plies and reaching calculation amount, mobile lithium metal ink head 2 to Adjacent subsequent region unit is printed, while protective layer ink head 4 is moved to the territory element just printed, carries out protective layer 9 Layer-by-layer printing, protective layer 9 print after the completion of, protective layer ink head 4 be moved to the printed subsequent region unit of metallic lithium layer 8 into Row printing, while gas forging idler wheel 32 is moved to the territory element that the printing of protective layer 9 is completed and carries out gas forging and stamping, until all areas list Member printing and gas forging and stamping completion, obtain metal lithium bands.
Detection is measured to the metal lithium bands of preparation, surfacing is uniform, and metallic lithium layer 8 is protected with a thickness of 21.0 μm Sheath 9 is with a thickness of 5.4 μm.
Embodiment 1 and implementation 2 have been all made of identical thickness control mode, i.e., then default thickness in monolayer passes through printing The number of plies controls the mode of print thickness.The advantage of this mode is to control more convenient, processing efficiency with higher, but It is, when printing thicker metallic lithium layer 8, it may appear that accumulated error.Therefore, the lithium layer 8 of relatively large thickness thickness instead is prepared Control precision may decrease.For this problem, the present invention has also been proposed second of thickness control mode, embodiment 3 Use such mode.
Embodiment 3
The lithium layer of 30 μ m-thicks, and the protective layer 9 of additional 5 μ m-thicks are printed on the copper foil tape with a thickness of 10 μm.
Using the 3D printer 1 with lithium metal ink head 2, protective layer ink head 4 and gas forging machine structure 3, and thickness inspection is set It surveys device in real time to detect printing cumulative thickness, sets the printing of lithium metal ink head 2 before printing on 3D printer 1 in advance and cover Cover 0.1mm2Square area, protective layer ink head 4 print overlay area and lithium metal ink head 2 it is completely the same, lithium metal ink head 2 Take with protective layer ink head 4 and presets 0.9 μm of initial monolayer print thickness respectively.
When printing, printing raw material is added in 3D printer 1, Li is selected2CO3As 9 raw material of protective layer, lithium metal is heated To 700 DEG C, 9 thickness of lithium layer 8 to be prepared and protective layer is inputted in 3D printer 1.Using the copper foil tape with a thickness of 10 μm It as substrate 7, is placed in support platform 6, printing environment applying argon gas is protected.Start to beat after the completion of preparation Print, firstly, positioning initiation region unit, lithium metal ink head 2 is directed at initiation region unit and carries out successively superposition printing, is printing It keeps lithium metal ink head 2 and substrate 7 to be in stationary state in journey, passes through thickness detection apparatus real-time monitoring while printing 8 thickness of lithium layer printed, and adjust single layer print thickness in real time accordingly, it is wanted when 8 thickness of the lithium layer superposition of local unit reaches After asking, mobile lithium metal ink head 2 to adjacent subsequent region unit is printed, while protective layer ink head 4 is moved to rigid printing Territory element, carry out the layer-by-layer printing of protective layer 9, the thickness control of protective layer 9 is carried out referring to the printing of lithium layer 8, protective layer 9 After the completion of printing, protective layer ink head 4 is moved to the printed subsequent region unit of metallic lithium layer 8 and is printed, while gas forging rolling Wheel 32 is moved to the territory element that the printing of protective layer 9 is completed and carries out gas forging and stamping, until all areas unit prints and gas has forged and pressed At acquisition metal lithium bands.
Detection is measured to the metal lithium bands of preparation, surfacing is uniform, and metallic lithium layer 8 is protected with a thickness of 31.2 μm Sheath 9 is with a thickness of 5.3 μm.
The thickness control mode of embodiment 3 is, by monitoring the cumulative thickness printed, prints in real time to the single of black head Thickness is adjusted, and by this multiple thickness control mode, controls the print thickness of each territory element more accurate, from Without accumulated error.But because of the thickness very little of single layer lithium layer 8, although using the black head of high-precision, to do Thickness to accurate adjustment single layer lithium layer 8 is still very difficult, and therefore, 8 overall thickness of lithium layer finally obtained still has centainly Error, the usual margin of error are lower than 5%.It is difficult to the case where adjusting control in real time for single layer print thickness, the present invention has also been proposed The third thickness control mode, following example 4 use this mode.
Embodiment 4
The lithium layer of 30 μ m-thicks, and the protective layer 9 of additional 5 μ m-thicks are printed on the copper foil tape with a thickness of 10 μm.
Using the 3D printer 1 with lithium metal ink head 2, protective layer ink head 4 and gas forging machine structure 3, and thickness inspection is set It surveys device to detect printing cumulative thickness, sets the printing covering of lithium metal ink head 2 on 3D printer 1 in advance before printing 0.1mm2Square area, protective layer ink head 4 print overlay area and lithium metal ink head 2 it is completely the same, 2 He of lithium metal ink head 1 μm of accurate single layer print thickness is respectively set in the expense of protective layer ink head 4.
When printing, printing raw material is added in 3D printer 1, Li is selected2CO3As 9 raw material of protective layer, lithium metal is heated To 800 DEG C, 9 thickness of lithium layer 8 to be prepared and protective layer is inputted in 3D printer 1, fixes tentatively the intended print number of plies accordingly. It using the copper foil tape with a thickness of 10 μm as substrate 7, is placed in support platform 6, printing environment applying argon gas is protected Shield.Start to print after the completion of preparation, firstly, positioning initiation region unit, lithium metal ink head 2 be aligned initiation region unit into Row successively superposition printing, keeps lithium metal ink head 2 and substrate 7 to be in stationary state, while printing in print procedure 8 thickness of lithium layer printed by thickness detection apparatus real-time monitoring, and the remaining printing number of plies of adjustment in real time accordingly, when local list After 8 thickness of the lithium layer superposition of member reaches requirement, mobile lithium metal ink head 2 to adjacent subsequent region unit is printed, simultaneously Protective layer ink head 4 is moved to the territory element just printed, carries out the layer-by-layer printing of protective layer 9, the thickness control reference of protective layer 9 The printing of lithium layer 8 carries out, and after the completion of protective layer 9 prints, protective layer ink head 4 is moved to the printed subsequent region of metallic lithium layer 8 Unit is printed, while gas forging idler wheel 32 is moved to the territory element that the printing of protective layer 9 is completed and carries out gas forging and stamping, until all Territory element printing and gas forging and stamping completion, obtain metal lithium bands.
Detection is measured to the metal lithium bands of preparation, surfacing is uniform, and metallic lithium layer 8 is protected with a thickness of 30.8 μm Sheath 9 is with a thickness of 5.2 μm.
The place that embodiment 4 is different from embodiment 3 is, by adjusting remaining printing times in printing in real time come more It is accurately controlled print thickness, for the single print thickness that control adjusts black head, regulation is more effective, without worry The precision problem of adjustment.In the ideal situation, the printing error of the mode of embodiment 4 can control one layer of print thickness with Interior, single layer print thickness is most thin up to 0.5 μm in experiment at present, that is to say, that lithium layer 8 and the theoretic throat error of protective layer 9 can Control is within 0.5 μm.But since other factors influence, verified by many experiments, under current experiment condition, thickness Actual error also can control within 0.8 μm.

Claims (12)

  1. The method that 1.3D printing prepares metal lithium bands, which comprises the steps of:
    A, the input lithium tape thickness to be prepared in 3D printer (1)；
    B, substrate (7) is divided into several territory elements to print, positions initiation region unit, in a protected environment, metal Lithium ink head (2) is directed at initiation region unit and carries out successively superposition printing, and lithium metal ink head (2) and substrate are made in print procedure (7) keep opposing stationary, lithium layer (8) thickness completes the printing of initiation region unit after being superimposed to preset thickness；
    C, mobile black head or substrate (7) make black head alignment subsequent region unit, under black head and substrate (7) opposing stationary situation The printing of subsequent region unit is carried out, until the printing of all areas unit is completed, obtains metal lithium bands.
  2. 2. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that set on 3D printer (1) Set protective layer ink head (4)；In b step and step c, after the completion of the printing of the lithium layer (8) of a territory element, protective layer ink is utilized Head (4) prints protective layer (9) on lithium layer (8).
  3. 3. the method that 3D printing as claimed in claim 2 prepares metal lithium bands, which is characterized in that the 3D printer (1) sets It is equipped with gas forging machine structure (3), the gas forging machine structure (3) includes drive link (31), gas forging idler wheel (32) and inert gas delivery pipe (33), gas forging idler wheel (32) is connected on drive link (31), gas forging idler wheel (32) if on be provided with dry gas forging hole, The inert gas delivery pipe (33) is connected with gas forging hole；
    In b step and step c, after the printing for completing territory element, lithium band is forged and pressed using gas forging machine structure (3), gas forging Idler wheel (32) is in contact with the protective layer (9) of territory element and micro-positive pressure is kept to be rolled, from inert gas delivery pipe (33) It is passed through constant temperature inert gas, inert gas forges hole by the gas that gas forges idler wheel (32) surface and carries out gas forging and stamping to territory element.
  4. 4. the method that 3D printing as claimed in claim 3 prepares metal lithium bands, which is characterized in that gas forging idler wheel (32) Rolling pressure is 10~100KPa, and the pressure of the gas forging and stamping is 1~15MPa.
  5. 5. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that pre- in 3D printer (1) If lithium layer (8) print thickness of single layer, calculates the printing number of plies according to the lithium tape thickness of input, passes through in b step and step c Control prints the number of plies of lithium layer (8) to control print thickness.
  6. 6. the method that 3D printing as claimed in claim 5 prepares metal lithium bands, which is characterized in that in b step and step c, By thickness detection apparatus lithium layer (8) cumulative thickness that has printed of monitoring and Real-time Feedback is to 3D printer (1), 3D printer (1) the remaining printing number of plies is adjusted according to monitoring data realize thickness control.
  7. 7. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that in b step and step c, By thickness detection apparatus lithium layer (8) cumulative thickness that has printed of monitoring and Real-time Feedback is to 3D printer (1), 3D printer (1) the printing number of plies is adjusted according to monitoring data and single layer print thickness realizes thickness control.
  8. 8. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that the territory element it is layer-by-layer In superposition printing, the territory element is rectangle, and the area of territory element is 0.005~0.1mm2Single layer print thickness is 0.5 ~1.0 μm.
  9. 9. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that prepared metal lithium bands Lithium layer (8) is with a thickness of 3~100 μm.
  10. 10. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that the lithium metal ink head (2) Interior lithium metal temperature is 300~1000 DEG C.
  11. 11. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that the protective layer ink head (4) Interior raw material is organic film class, salts or solid electrolyte class, and the organic film class is fluorine dragon, polyethylene, polypropylene, poly- ammonia Ester or polytetrafluoroethylene (PTFE), the salts are Li2CO3Or Li3PO4, the solid electrolyte class be LPON, NASICON or Sulfide.
  12. 12. the method that 3D printing as described in claim 1 prepares metal lithium bands, which is characterized in that the substrate (7) is copper Foil, aluminium foil, rustless steel foil, aluminum plastic film, nylon membrane, polyethylene film, polypropylene screen, polychloroethylene film, polyester film or graphite are negative Pole band.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6036631A (en) * 1983-08-08 1985-02-25 Sumitomo Light Metal Ind Ltd Production of aluminum alloy casting ingot
CN1400107A (en) * 2001-08-03 2003-03-05 中国科学院金属研究所 Ink jet printing method for preparing metal oxide functional film
CN105932227A (en) * 2016-05-27 2016-09-07 佛山市智巢电子科技有限公司 Method for preparing nano-electrode film of lithium ion battery through ink-jet printing
CN106217875A (en) * 2016-08-03 2016-12-14 富士胶片电子材料（苏州）有限公司 The forming method of quartz container protecting film
CN106274111A (en) * 2016-08-04 2017-01-04 郭云岐 The full-color painting methods that a kind of 3D prints

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6036631A (en) * 1983-08-08 1985-02-25 Sumitomo Light Metal Ind Ltd Production of aluminum alloy casting ingot
CN1400107A (en) * 2001-08-03 2003-03-05 中国科学院金属研究所 Ink jet printing method for preparing metal oxide functional film
CN105932227A (en) * 2016-05-27 2016-09-07 佛山市智巢电子科技有限公司 Method for preparing nano-electrode film of lithium ion battery through ink-jet printing
CN106217875A (en) * 2016-08-03 2016-12-14 富士胶片电子材料（苏州）有限公司 The forming method of quartz container protecting film
CN106274111A (en) * 2016-08-04 2017-01-04 郭云岐 The full-color painting methods that a kind of 3D prints

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