CN110406137A - A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery - Google Patents
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery Download PDFInfo
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- CN110406137A CN110406137A CN201910563280.XA CN201910563280A CN110406137A CN 110406137 A CN110406137 A CN 110406137A CN 201910563280 A CN201910563280 A CN 201910563280A CN 110406137 A CN110406137 A CN 110406137A
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- Prior art keywords
- preparation
- annealing
- temperature
- lithium ion
- ion battery
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29D—PRODUCING PARTICULAR ARTICLES FROM PLASTICS OR FROM SUBSTANCES IN A PLASTIC STATE
- B29D7/00—Producing flat articles, e.g. films or sheets
- B29D7/01—Films or sheets
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
-
- 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
Abstract
The invention discloses a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-heat it is compound-drawing and setting.The present invention by using curtain coating film preparation-annealing-heat it is compound-preparation method of drawing and setting, and the parameter of each preparation step in-process of strict control, so that the product porosity prepared, puncture strength, vertical tensile strength and high temperature percent thermal shrinkage are all very outstanding, and the preparation method is simple, it is lower to equipment requirement, condition is easy to control, and is suitble to industrialization development trend.
Description
Technical field
The present invention relates to high molecular material plastic film field, in particular to a kind of high porosity polyolefin lithium ion battery
The preparation method of diaphragm.
Background technique
As the development quick charging battery of lithium ion battery has started to be widely available exploitation, and in the big material of lithium ion battery four
One of the development need of its high porosity polyolefin diaphragm of lithium ion battery further improve, due to polyolefin lithium ion battery
Diaphragm porosity distribution upper-bound theory is 55%, and preparation method needs kinds of processes parameter coordination.
At present high multiplying power lithium ion battery mainly from material nano, improve electrolytic conductivity and diaphragm porosity come into
Row improves, and diaphragm is between positive and negative anodes, and lithium ion is from positive deintercalation, and solvation, is then entered by diaphragm negative in the electrolytic solution
Extremely, solvent is gone to be embedded in cathode, whole process septation inhibition is big, and raising diaphragm porosity can greatly improve forthright again
Energy.
Polyolefin lithium ion battery porosity distribution is 45% or so at this stage, using cannot be real in terms of quick charging battery
Its existing real effect, it is necessary to it produces 50% or more porosity polyolefin diaphragm of lithium ion battery and is just able to satisfy its fast charge effect,
Therefore the growth requirement that high porosity polyolefin diaphragm of lithium ion battery is market is prepared.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of method is simple, lower to equipment requirement, condition is easy to control,
It is suitble to industrialization development trend, and the height that the high puncture strength of product, high tensile and the high temperature lower shrinkage prepared is good
The preparation method of porosity polyolefin diaphragm of lithium ion battery.
In order to solve the above-mentioned technical problem, the technical solution of the present invention is as follows:
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 220-230 DEG C, 225 DEG C of runner temperature, die head by PP GRANULES investment extruder temperature
It is squeezed out in 210 DEG C of temperature, the production extrusion system that slab temperature is 90-100 DEG C and speed of production is 90m/min, then
Collect monolayer cast film；
2. annealing: it is 110-120 that the monolayer cast film being prepared, which is put into annealing device, and carries out annealing temperature
DEG C and annealing time be 12-18h annealing；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 20-30%, hot-drawn
At the drawing and setting that temperature is 120-130 DEG C, hot-draw ratio 220-250%, retraction ratio are 25% and setting temperature is 150 DEG C
Reason, obtains lithium ion battery separator.
Preferably, the monolayer cast film is with a thickness of 8.9 μm.
Preferably, with a thickness of 16 μm after the lithium battery diaphragm drawing and setting.
Preferably, the recombination velocity in the hot combined processing is 5m/min.
Preferably, monolayer cast film elastic recovery rate >=90%.
Beneficial effects of the present invention:
The present invention by using curtain coating film preparation-annealing-heat it is compound-preparation method of drawing and setting, and strictly
The parameter of each preparation step in-process is controlled, so that the product porosity prepared, puncture strength, vertical tensile strength and high temperature
Percent thermal shrinkage is all very outstanding, and the preparation method is simple, and lower to equipment requirement, condition is easy to control, and is suitble to industrialization
Development trend.
Detailed description of the invention
Fig. 1 is preparation method flow chart of the invention.
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing.It should be noted that for
The explanation of these embodiments is used to help understand the present invention, but and does not constitute a limitation of the invention.In addition, disclosed below
The each embodiment of the present invention involved in technical characteristic can be combined with each other as long as they do not conflict with each other.
According to Fig. 1:
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 220-230 DEG C, 225 DEG C of runner temperature, die head by PP GRANULES investment extruder temperature
It is squeezed out in 210 DEG C of temperature, the production extrusion system that slab temperature is 90-100 DEG C and speed of production is 90m/min, then
Collect monolayer cast film；
2. annealing: it is 110-120 that the monolayer cast film being prepared, which is put into annealing device, and carries out annealing temperature
DEG C and annealing time be 12-18h annealing；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 20-30%, hot-drawn
At the drawing and setting that temperature is 120-130 DEG C, hot-draw ratio 220-250%, retraction ratio are 25% and setting temperature is 150 DEG C
Reason, obtains lithium ion battery separator.
The monolayer cast film is with a thickness of 8.9 μm.
With a thickness of 16 μm after the lithium battery diaphragm drawing and setting.
Recombination velocity in the hot combined processing is 5m/min.
Monolayer cast film elastic recovery rate >=90%.
In order to more preferably illustrate preparation method of the present invention, Singapore TPC high crystallinity polypropylenes particulate feed material, board are selected
It number is FS2014, melt index is 2.6 ± 0.2 to carry out proportion explanation.
Case study on implementation 1
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 220 DEG C, 225 DEG C of runner temperature, die head temperature by PP GRANULES investment extruder temperature
210 DEG C, squeezed out in the production extrusion system that slab temperature is 90 DEG C and speed of production is 90m/min, then collect single layer
Casting films；
2. annealing: will the monolayer cast film that be prepared put into annealing device in carry out annealing temperature be 110 DEG C and
Annealing time is the annealing of 12h；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 20%, hot-drawn temperature
For 120 DEG C, hot-draw ratio 220%, the processing of retraction ratio is 25% and setting temperature is 150 DEG C drawing and setting, obtain lithium from
Sub- battery diaphragm.
Case study on implementation 2
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 230 DEG C, 225 DEG C of runner temperature, die head temperature by PP GRANULES investment extruder temperature
210 DEG C, squeezed out in the production extrusion system that slab temperature is 100 DEG C and speed of production is 90m/min, then collect single layer
Casting films；
2. annealing: will the monolayer cast film that be prepared put into annealing device in carry out annealing temperature be 120 DEG C and
Annealing time is the annealing of 18h；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 30%, hot-drawn temperature
For 130 DEG C, hot-draw ratio 250%, the processing of retraction ratio is 25% and setting temperature is 150 DEG C drawing and setting, obtain lithium from
Sub- battery diaphragm.
Case study on implementation 3
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 225 DEG C, 225 DEG C of runner temperature, die head temperature by PP GRANULES investment extruder temperature
210 DEG C, squeezed out in the production extrusion system that slab temperature is 95 DEG C and speed of production is 90m/min, then collect single layer
Casting films；
2. annealing: will the monolayer cast film that be prepared put into annealing device in carry out annealing temperature be 115 DEG C and
Annealing time is the annealing of 15h；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 25%, hot-drawn temperature
For 125 DEG C, hot-draw ratio 235%, the processing of retraction ratio is 25% and setting temperature is 150 DEG C drawing and setting, obtain lithium from
Sub- battery diaphragm.
Case study on implementation 4
A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-
Hot compound-drawing and setting:
1. being cast film preparation: being 230 DEG C, 225 DEG C of runner temperature, die head temperature by PP GRANULES investment extruder temperature
210 DEG C, squeezed out in the production extrusion system that slab temperature is 93 DEG C and speed of production is 90m/min, then collect single layer
Casting films；
2. annealing: will the monolayer cast film that be prepared put into annealing device in carry out annealing temperature be 118 DEG C and
Annealing time is the annealing of 14h；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films that the superposition number of plies is two layers are put into
The hot combined processing that combined temp is 80 DEG C is carried out in set composite, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 23%, hot-drawn temperature
For 123 DEG C, hot-draw ratio 230%, the processing of retraction ratio is 25% and setting temperature is 150 DEG C drawing and setting, obtain lithium from
Sub- battery diaphragm.
In order to which the product more preferably obtained with this preparation method compares, following comparative's case is enumerated thus:
Compare case 1
Directly acquire the PP high porosity single layer microporous film with a thickness of 16um.
Compare case 1
Directly acquire the PP high porosity composite micro porous film with a thickness of 16um.
The obtained lithium ion battery separator of above-mentioned case study on implementation 1-4 is measured into its thickness, air penetrability, porosity, is stretched by force
The data and comparison case data that degree, puncture strength and thermal stability index measure are as shown in the table:
Table 1
Each testing performance index standard of upper table is as follows:
| Detection project | Unit | Testing standard |
| Thickness | μm | GB/T6672-2001 |
| Air permeability | sec/100ml | GB/T36363-2018 |
| Porosity | % | GB/T36363-2018 |
| Tensile strength | kgf/cm2 | GB/T36363-2018 |
| Puncture strength | gf | GB/T36363-2018 |
| It is heat-shrinked (120 DEG C/1h) | % | GB/T10003-2008 |
Table 2
Embodiment 1-4 and comparative example 1-2 compares it can be seen that embodiment 1-4 can using the technological parameter of design from table 1
The high porosity polyolefin diaphragm of lithium ion battery for preparing 16 μm takes technique to prepare product reachable with porosity
52%, so that the product porosity prepared, puncture strength, vertical tensile strength and high temperature percent thermal shrinkage are all very outstanding, and
The preparation method is simple, lower to equipment requirement, and condition is easy to control, and is suitble to industrialization development trend.
And comparing case 1 is single layer high porosity microporous barrier, with certain porosity and and air permeability, but porosity is remote
The requirement of client is far not achieved, puncture strength, vertical tensile strength are higher compared with low and high temperature percent thermal shrinkage.
And comparing case 2 is compound high porosity microporous barrier, with certain porosity and and air permeability, but porosity is remote
The requirement of client is far not achieved.
In conjunction with attached drawing, the embodiments of the present invention are described in detail above, but the present invention is not limited to described implementations
Mode.For a person skilled in the art, in the case where not departing from the principle of the invention and spirit, to these embodiments
A variety of change, modification, replacement and modification are carried out, are still fallen in protection scope of the present invention.
Claims (5)
1. a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery, including curtain coating film preparation-annealing-heat
Compound-drawing and setting, it is characterised in that:
1. being cast film preparation: being 220-230 DEG C, 225 DEG C of runner temperature, die head temperature by PP GRANULES investment extruder temperature
210 DEG C, squeezed out in the production extrusion system that slab temperature is 90-100 DEG C and speed of production is 90m/min, then collect
Monolayer cast film；
2. annealing: will the monolayer cast film that be prepared put into annealing device in carry out annealing temperature be 110-120 DEG C and
Annealing time is the annealing of 12-18h；
3. hot compound: the monolayer cast film after annealing being superimposed, so that the casting films investment that the superposition number of plies is two layers is compound
The hot combined processing that combined temp is 80 DEG C is carried out in device, obtains composite membrane；
4. drawing and setting: composite membrane is successively carried out using cold drawing temperature is 40 DEG C, cold stretch ratio is 20-30%, hot-drawn temperature
It is handled for 120-130 DEG C, hot-draw ratio 220-250%, the drawing and setting that retraction ratio is 25% and setting temperature is 150 DEG C,
Obtain lithium ion battery separator.
2. a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery according to claim 1, feature exist
In: the monolayer cast film is with a thickness of 8.9 μm.
3. a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery according to claim 1, feature exist
In: with a thickness of 16 μm after the lithium battery diaphragm drawing and setting.
4. a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery according to claim 1, feature exist
In: the recombination velocity in the hot combined processing is 5m/min.
5. a kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery according to claim 1, feature exist
In: monolayer cast film elastic recovery rate >=90%.
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| CN201910563280.XA CN110406137A (en) | 2019-06-26 | 2019-06-26 | A kind of preparation method of high porosity polyolefin diaphragm of lithium ion battery |
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Cited By (1)
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