A review on the preparation of ultra-low-temperature， high-temperature， and cross-temperature zone phase change materials and the regulation of physical properties

doi:10.19799/j.cnki.2095-4239.2023.0726

Abstract

Abstract:

Phase change energy storage technology harnesses the unique properties of phase change materials to release or absorb latent heat during phase transitions, enabling energy storage in the form of latent heat. This technology holds promising applications in electric vehicles, renewable energy storage, grid peaking, and smart grids owing to its high energy density, extended lifespan, and high power. It presents a viable solution for energy transition and efficient energy utilization. This paper delves into the advantages, disadvantages, and application scopes of phase change materials within various temperature zones: ultra-low (-190 ℃ to -50 ℃), low (-50 ℃ to 0 ℃), general (0 ℃ to 100 ℃), and high (100 ℃ to 700 ℃) temperatures. This categorization is based on an exploration of the pertinent literature. To enhance phase change material properties, methods including thermal conductivity enhancement, subcooling reduction, phase change temperature regulation, and improvement of cycling stability are discussed in this study. Moreover, it examines the preparation methods of composite phase change materials, introducing microencapsulation, impregnation, sol-gel, and ultrasonic methods, while elucidating the drawbacks of the latter three methods. Finally, it envisions potential future applications of phase change materials, aiming to serve as a reference and guide for further research in the domain of energy storage using phase change energy storage technology.

Key words: phase change material, phase change energy storage, physical regulation, preparation method

CLC Number:

TB 333

Xiaohui SHE, Xingyu WANG, Xiaolong GUO, Yixuan LIU, Jiayun WANG, Peng Han, Xiaofen REN, Xuemin ZHAO. A review on the preparation of ultra-low-temperature， high-temperature， and cross-temperature zone phase change materials and the regulation of physical properties[J]. Energy Storage Science and Technology, 2023, 12(12): 3818-3835.

Figures/Tables 17

Fig. 1

Table 1

Table 2

Ultra-low temperature organic phase change materials"

材料名称	材料类型	相变温度/K	相变潜热 /(kJ/kg)	导热系数 /[W/(m·K)]	密度/(kg/m³)	比热容/[J/(kg·K)]
C₃H₈(丙烷)	固液-有机	-186.67	79.6	0.21～0.13(l) (-186.67～-42.12)	732～581(l) (-186.67～-42.12)	1.87～2.25(l) (-186.67～-42.12)
C₄H₈(1-丁烯)	固液-有机	-185.35	68.58	0.22～0.13(l) (-137.25～-0.49)	734.1～581(l) (-137.25～-0.49)	1.97～2.31(l) (-137.25～-0.49)
C₃H₆(丙烯)	固液-有机	-185.15	71.29	0.18～0.15(l) (-173.15～-47.69)	754.9～609.1(l) (-173.15～-47.69)	0.85～1.29(s)(-223～-193) 1.81～2.18(l)(-173.15～-47.69)
CH₄(甲烷)	固液-有机	-182.5	58.43	0.21～0.18(l) (-181.46～161.48)	450～422(l) (-181.46～161.48)	3.37～3.48(l)(-181.46～161.48)
C₅H₁₂(异戊烷)	固液-有机	-160.15	71.1	0.187～0.117(l) (-160～0)	787.8～639.9(l) (-160～0)	1.87～2.21(l)(-160～0)
C₆H₁₄(2-甲基戊烷)	固液-有机	-153.15	72.76	0.144～0.114(l) (-153～0)	807～671(l) (-153～0)	1.77～2.12(l)(-153～0)
C₅H₈(异戊二烯)	固液-有机	-142.15	72.22	0.18～0.13(l) (-143～0)	854～843(s) (-170～-158)	0.95～1.08(s)(-174～-158) 1.8～2.1(l)(-143～0)
C₂H₆O(二甲醚)	固液-有机	-141.5	107.23	0.24～0.18(l) (-123～25)	753(l) (-25)	2.22(l)(-33)
C₄H₁₀(丁烷)	固液-有机	-137.15	80.2	0.18～0.12(l) (-138～-1)	735～602(l) (-138～-1)	1.97～2.31(l)(-138～-1)
C₅H₁₂(戊烷)	固液-有机	-129.75	116.43	0.173～0.121(l) (-123～0)	756～645(l) (-123～0)	1.97～2.21(l)(-123～0)
C₃H₆(环丙烷)	固液-有机	-127.15	-129.28	0.136(l) (-37)	733～678(l)(-79～-34)	1.93(l) (-33)
C₂H₆O(乙醇)	固液-有机	-114.35	108.53	0.167(l) (25)	826～807(l) (-25～0)	1.02～1.38(s)(-173～-123) 2.02～2.27(l)(-25～0)
CH₃OH(甲醇)	固液-有机	-97.15	99.25	0.210～0.206	904～810	2.20～2.40
C₆H₁₄(正己烷)	固液-有机	-95.15	151.78	0.156～0.135	760～677	1.88～2.15
C₅H₁₀(环戊烷)	固液-有机	-93.95	8.56	0.143	751	1.42～1.69
CH₃NH₂(甲胺)	固液-有机	-93.15	197.38	0.219	700	3.19～3.26
C₇H₁₆(正庚烷)	固液-有机	-90.55	140.12	0.156～0.138	—	1.96～2.15
C₄H₆O(甲基乙基甲酮)	固液-有机	-86.65	177.05	0.17～0.15	826	2.07～2.16
E-65	固液-有机	-65	240	—	—	—
C₈H₁₈(正辛烷)	固液-有机	-56.85	181.57	0.15～0.13	761～718	2.02～2.14
C₆H₁₂O(3-己酮)	固液-有机	-55.65	134.5	0.17～0.16	833	2.05～2.12
C₆H₁₀O₂(2-己酮)	固液-有机	-55.45	148.7	0.16～0.15	830	2.02～2.08
C₉H₂₀(正壬烷)	固液-有机	-53.65	117	0.15～0.13	773～734	1.99～2.12
CH₄(甲烷)	液气-有机	-161.48	510.83	0.012～0.003(g)(-161.48～0)	1.82～0.72(g) (-161.48～0)	2.22～2.18(g) (-161.48～0)
CH₃CH₃(乙烷)	液气-有机	-88	489	0.25～0.17	641～544	2.33～2.43
C₂H₂(乙炔)	液气-有机	-84.15	144	0.02	764.3～760.2	1.37

Table 2

Table 3

Table 4

Low-temperature phase change material"

名称	类型	相变温度/℃	相变潜热 /(kJ/kg)	导热系数 /[W/(m·K)]	密度(组分比) /(kg/m³)	比热容 /[J/(kg·K)]	腐蚀性
30.5% CaCl₂	共晶	-49.5	76.81	—	30.5%(质量比)	—	—
CuCl₂ 水溶液(29.8%)	共晶	-40	166.17	—	29.8%(体积比)	—	—
汞	无机物	-39	11.4	—	13590	—	—
3-庚酮 C₇H₁₄O	有机物	-37.1	153.5	0.15～0.14	822	—	—
K₂CO₃水溶液(39.6%)	共晶	-36.5	165.36	—	39.6%(体积比)	—	—
2-庚酮 C₇H₁₄O	有机物	-35	172.6	0.15～0.14	851～834	—	—
MgCl₂水溶液(17.1%)	共晶	-33.6	221.86	—	17.1%(体积比)	—	—
21.01% MgCl₂	共晶	-33.5	36.3	—	21.01%(质量比)	—	—
Al(NO₃)₃ 水溶液 (30.5%)	共晶	-30.6	207.63	—	30.5%(体积比)	—	—
癸烷 C₁₀H₂₂	有机物	-29.7	202	0.1311	735	2220	—
硝酸镁Mg(NO₃)₂+水	共晶	-29	187	—	34.6∶65.4(质量比)	—	—
Mg(NO₃)₂ 水溶液(34.6%)	共晶	-29	186.93	—	34.6%(体积比)	—	—
Zn(NO₃)₂ 水溶液(39.4%)	共晶	-29	169.88	—	39.4%(体积比)	—	有
NH₄F水溶液(32.3%)	共晶	-28.1	187.83	—	32.3%(体积比)	—	有
NaBr水溶液(40.3%)	共晶	-28	175.69	—	40.3%(体积比)	—	—
乙二醇+氯化铵+水	共晶	-23	176	—	10∶15∶75(质量比)	—	有
27.9% NaCl	共晶	-23	26.1	—	27.9%(体积比)	—	—
KF水溶液(21.5%)	共晶	-21.6	227.13	—	21.5%(体积比)	—	有
NaCl水溶液(22.4%)	共晶	-21.2	228.14	—	22.4%(体积比)	—	—
共晶组成的氯化钠水溶液(23.3%)	共晶	-21.1	246.6	—	23.3 %(质量比)	—	—
氯化钠NaCl+水	共晶	-21	228	—	22.4∶77.6(质量比)	—	—
MgCl₂水溶液(25%)	共晶	-19.4	223.1	—	25%(体积比)	—	—
(NH₄)₂SO₄ 水溶液(39.7%)	共晶	-18.5	187.75	—	29.7%(体积比)	—	有
NaNO₃水溶液(36.9%)	共晶	-17.7	187.79	—	36.9%(体积比)	—	有腐蚀性，受猛烈撞击或受热爆炸性分解
NH₄NO₃水溶液(41.2%)	共晶	-17.35	186.29	—	41.2%(体积比)	—	有
Ca(NO₃)₂ 水溶液(35%)	共晶	-16	199.35	—	35%(体积比)	—	—
NH₄Cl水溶液(19.5%)	共晶	-16	248.44	—	19.5%(体积比)	—	有
甘油C₃H₈O₃+醋酸钠+水	共晶	-14	172	—	10∶10∶80(质量比)	—	—
K₂HPO₄水溶液(36.8%)	共晶	-13.5	197.79	—	36.8%(体积比)	—	—
氯化钾+水	共晶	-11	253	—	19.5∶80.5(质量比)	—	—
Na₂S₂O₃ 水溶液(30%)	共晶	-11	219.86	—	30%(体积比)	—	—
KCl水溶液 (19.5%)	共晶	-10.7	253.18	—	19.5%(体积比)	—	—
MnSO₃水溶液(32.2%)	共晶	-10.5	213.07	—	32.2%(体积比)	—	—
二乙二醇C₄H₁₀O₃	有机物	-10	247	—	1118	—	—
NaH₂PO₄ 水溶液(23.4%)	共晶	-9.9	214.25	—	23.4%(体积比)	—	—
十二烷+十三烷	有机物	-9.7	159	—	60∶40(体积比)	—	—
正十二烷 C₁₂H₂₆	有机物	-9.6	216	0.134	745.64	2039	—
十二烷+十三烷	有机物	-9.1	145	—	50∶50(体积比)	—	—
十二烷+十三烷	有机物	-8	147	—	40∶60(体积比)	—	—
BaCl₂水溶液(22.5%)	共晶	-7.8	246.44	—	22.5%(体积比)	—	—
22.1% BaCl₂	共晶	-7.7	10.2	—	22.1 %(质量比)	—	—
三乙二醇 C₆H₁₄O₄	有机物	-7	247	—	1200	—	—
ZnSO₃水溶液(27.2%)	共晶	-6.5	235.75	—	27.2%(体积比)	—	—
Sr(NO₃)₂水溶液(24.5%)	共晶	-5.75	243.15	—	24.5%(体积比)	—	—
十二烷+十三烷	有机物	-5.4	126	—	20∶80(体积比)	—	—
KHCO₃水溶液(16.95%)	共晶	-5.4	268.54	—	16.95%(体积比)	—	—
十三烷 C₁₃H₂₈	有机物	-5.35	154	0.131	750	1979	—
18.63% MgSO₄	共晶	-4.8	84.96	—	18.63%(质量比)	—	—
NiSO₄水溶液(20.6%)	共晶	-4.15	258.61	—	20.6%(体积比)	—	—
硫酸钠+水	共晶	-4	285	—	12.7∶87.3(质量比)	—	—
乳酸钙+氯化铵	共晶	-4	265	—	50∶50(质量比)	—	有
MgSO₄水溶液(19%)	共晶	-3.9	264.42	—	19%(体积比)	—	—
Na₂SO₄水溶液(12.7%)	共晶	-3.55	284.95	—	12.7%(体积比)	—	—
NaF水溶液(3.9%)	共晶	-3.5	314.09	—	3.9%(体积比)	—	有
山梨酸钾C₆H₇O₂K+氯化钾	共晶	-3	255	—	85.72∶14.28(质量比)	—	—
KNO₃水溶液(9.7%)	共晶	-2.8	296.02	—	9.7%(体积比)	—	—
Na₂CO₃水溶液(5.9%)	共晶	-2.1	310.23	—	5.9%(体积比)	—	有
FeSO₄水溶液(13%)	共晶	-1.8	286.81	—	13%(体积比)	—	—
CuSO₄水溶液(11.9%)	共晶	-1.6	290.91	—	11.9%(体积比)	—	—
十三烷+十四烷	有机物	-1.5	110	—	80∶20(体积比)	—	—
4.03% Na₂SO₄	共晶	-1.2	1.07	—	4.03%(质量比)	—	—
十三烷+十四烷	有机物	-0.5	138	—	60∶40(体积比)	—	—
冰	无机物	0	333	0.598	998.75	4137	—

Table 4

Table 5

Table 6

Table 7

Table 8

Thermal properties of commercial phase change materials"

名称	类型	相变温度/℃	相变焓/(kJ/kg)	导热系数/[W/(m·K)]	密度/(kg/m³)	比热容/[kJ/(kg·K)]	体积膨胀比/%	闪点/℃
RTO	有机	0	175	0.2	770(液) 880(固)	2	12.5	110
A2	有机	1	230	—	—	—	—	—
ATP2	有机	2	215	—	—	—	—	—
RT2 HC	有机	2	200	0.2	770(液) 880(固)	2	12.5	>100
RT3 HC	有机	3	190	0.2	770(液) 880(固)	2	12.5	>110
A3	有机	3	230	—	—	—	—	—
RT4	有机	4	175	0.2	770(液) 880(固)	2	12.5	110
A4	有机	4	235	—	—	—	—	—
Pure Temp4	有机	5	187	—	—	—	—	—
RT5	有机	5	180	0.2	770(液) 880(固)	2	12.5	113
RT8	有机	8	175	0.2	770(液) 880(固)	2	14	116
RT8HC	有机	8	190	0.2	770(液) 880(固)	2	12.5	120
RT10	有机	10	165	0.2	770(液) 880(固)	2	12.5	123
RT10HC	有机	10	200	0.2	770(液) 880(固)	2	12.5	130
RT11HC	有机	11	200	0.2	770(液) 880(固)	2	12.5	130
RT12	有机	12	164	0.2	770(液) 880(固)	2	12.5	125
RT15	有机	15	155	0.2	770(液) 880(固)	2	12.5	130
RT18HC	有机	18	260	0.2	770(液) 880(固)	2	12.5	135
RT21	有机	21	165	0.2	770(液) 880(固)	2	12.5	140
RT21HC	有机	21	190	0.2	770(液) 880(固)	2	14	140
RT22HC	有机	22	190	0.2	700(液) 760(固)	2	12.5	>150
RT24HC	有机	24	200	0.2	700(液) 800(固)	2	12	150
RT25HC	有机	25	230	0.2	770(液) 880(固)	2	12.5	150
RT28HC	有机	28	250	0.2	770(液) 880(固)	2	12.5	165
RT31	有机	31	165	0.2	760(液) 880(固)	2	12.5	157
RT35	有机	35	160	0.2	770(液) 860(固)	2	12.5	170
RT35HC	有机	35	240	0.2	770(液) 880(固)	2	12	177
RT38	有机	38	170	0.2	750(液) 880(固)	2	12.5	165
RT42	有机	42	165	0.2	760(液) 880(固)	2	12.5	186
RT44HC	有机	44	250	0.2	700(液) 800(固)	2	12.5	>180
RT47	有机	47	160	0.2	770(液) 880(固)	2	12	>180
RT50	有机	50	160	0.2	760(液) 880(固)	2	12.5	>200
RT54HC	有机	54	200	0.2	800(液) 850(固)	2	—	—
RT55	有机	55	170	0.2	770(液) 880(固)	2	14	>200
RT60	有机	60	160	0.2	770(液) 880(固)	2	12.5	>200
RT62HC	有机	62	230	0.2	840(液) 850(固)	2	—	—
RT65	有机	65	150	0.2	780(液) 880(固)	2	11.3	>200
RT69HC	有机	69	230	0.2	840(液) 940(固)	2	—	—
RT70HC	有机	70	260	0.2	770(液) 880(固)	2	12.5	227
RT82	有机	82	170	0.2	770(液) 880(固)	2	12.5	>200
RT80HC	有机	78	220	0.2	800(液) 900(固)	2	—	—
RT90HC	有机	90	170	0.2	850(液) 950(固)	2	—	—
RT100HC	有机	100	180	0.2	850(液) 1000(固)	2	15	>250
RT100	有机	100	120	0.2	770(液) 880(固)	2	12.5	312

Table 8

Table 9

Table 10

Table 11

Table 12

Fig. 2

Table 13

Table 14

Table 15

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储能技术	储能规模/MW	储能周期	储能密度/(GJ/m³)	效率/%	寿命	成本/(元/kWh)
显热技术	0.001～10	数小时～数天	<0.2	75～97	长	10～150
潜热技术	0.001～1	数小时～数周	0.3～0.5	65～85	中	200～500
热化学技术	0.001～1	数天～数月	0.5～3	45～75	中短	500～1000

材料名称	材料类型	相变温度/℃	相变潜热/(kJ/kg)	导热系数/[W/(m·K)]	密度/(kg/m³)
石蜡C13～C24	有机	22～24	189	0.21	900
石蜡C18	有机	27.5	243.5	0.385	774
石蜡C16～C28	有机	42～44	189	0.21	910
石蜡C20～C33	有机	48～50	189	0.21	912
石蜡C22～C45	有机	58～60	189	0.21	920
切片石蜡	有机	64	266	0.346	916
石蜡C21～C50	有机	66～68	189	0.212	930

材料名称	材料类型	相变温度/℃	相变潜热/(kJ/kg)	导热系数/[W/(m·K)]	密度/(kg/m³)	比热容/[J/(kg·K)]	成分
Li	金属	180.7	435	84	534	3580	100
Mg-Zn	共熔	340	185	—	—	—	46.3∶53.7
Zn-Al	共熔	381	138	—	—	—	96∶4
Al-Si-Sb	共熔	471	471	—	—	—	86.4∶9.4∶4.2
Mg-Al	合金	497	285	—	—	—	34.65∶65.35
Al-Cu-Mg	共熔	506	365	—	—	—	60.8∶33.2∶6
Al-Si-Cu-Mg	共熔	507	374	—	—	—	64.1∶5.2∶28∶2.2
Al-Si-Cu	共熔	525	364	—	—	—	68.5∶26.5∶26.5
Al-Cu	共熔	548	372	—	—	—	66.92∶33.08
Al-Si-Mg	共熔	555	485	—	—	—	83.14∶11.7∶5.16
Al-Si	合金	557	498	—	—	—	87.76∶12.24
Al-Si-Cu	共熔	571	406	—	—	—	46.3∶4.6∶49.1
Mg	金属	650	365	156	1740	1270	100
Al	金属	660	398	217	2700	880	100
Zn-Mg	共熔	342	155	75	2850	730	51∶49
Mg-Al	共熔	497	285	—	2155	—	34.65∶65.35
Al-Cu-Mg-Zn	—	520	305	—	3140	1510(液) 1130(固)	54∶22∶18∶6
Al-Si	合金	576	560	160	2700	1038(液) 1741(固)	88∶12
Zn-Cu-Mg	合金	703	176	—	8670	420	49∶45∶6
Al-Cu-Sb	共熔	545	331	—	4000	—	64.3∶34∶1.7
Al-Cu	共熔	548	372	—	3600	—	66.92∶33.08

相变材料	成核剂	成核剂浓度	过冷度减少率/%
CaCl₂·6H₂O	BaI₂·6H₂O	0.5	100
	K₂CO₃	0.5	50
	SrCl₂·6H₂O	0.1	58.2
	SrBr₂·6H₂O	1	90.7
KF·4H₂O	SiO₂	—	51.3
LiNO₃·3H₂O	Cu₃(OH)₅(NO₃)·2H₂O	0.1	87
MgCl₂·6H₂O	Ba(OH)₂	0.5	100
Na₂SO₄·10H₂O	Na₂B₄O₇·10H₂O	1.9	78.8
C₄H₁₀O₄	C₇H₁₀CaO₄	1	64.5
C₅H₁₂O₄	AlN(50 nm)	3	76
Na₂HPO₄·12H₂O	Al(8.5～20 μm铝粉)	3.7	67.5

外壳材料	芯材	方法	相变温度
聚甲基丙烯酸甲酯(PMMA)	十八烷(C18)	悬浮聚合法	24.7 ℃
六亚甲基二异氰酸酯(HDI)， 1,3-丙二胺	十二醇	界面聚合法	24.47 ℃
三聚氰胺甲醛树脂	十四烷	原位聚合法	75 ℃
碳酸钙	N-十八烷+CaCl₂(40∶60质量)	自组装法	28.22 ℃
苯乙烯-甲基丙烯酸甲酯共聚物	正十八烷	微乳液原位聚合法	∆H_m 107.9 kJ/kg; ∆H_c 104.9 kJ/kg
聚苯乙烯	十九烷	两步皮克林乳化程序	T_m 34.12 ℃; T_c 29.97 ℃