固-固相变储热材料的研究进展

doi:10.16085/j.issn.1000-6613.2020-0875

摘要/Abstract

摘要：

与固-液相变材料相比，固-固相变材料（SS-PCMs）受到的关注较少；鉴于SS-PCMs具有储能密度高、无毒且腐蚀性小、相变时无液体产生且体积变化较小、不易发生相分离以及过冷度小等优点，因而是一类具有发展潜力的相变材料。本文基于SS-PCMs的研究现状，对近年来几类重要SS-PCMs如多元醇SS-PCMs、高分子类SS-PCMs及无机盐类SS-PCMs的研究进展进行了综述。简要阐述了SS-PCMs的分类以及各类SS-PCMs的性能、相变储热机制和优缺点。同时介绍了选择固-固相变材料应用时的基本原则，并针对相变材料热导率低，过冷度大、稳定性差等问题的改性研究进行了综述，还简要综述了SS-PCMs的应用研究。最后指出，未来的研究应着眼于解决已合成SS-PCMs的缺陷，开发多功能的SS-PCMs，并在SS-PCMs的实际应用方面实现突破。

关键词: 储热技术, 潜热储热, 固-固相变材料, 相变储热机制, 热导率, 过冷度, 稳定性

Abstract:

Compared with solid-liquid phase change materials, solid-solid phase change materials (SS-PCMs) have received less attention. SS-PCMs is a type of phase change material with development potential as they possess the advantages of high energy storage density, non-toxic and low corrosion, no liquid generated and small volume change during phase change, low phase separation, and low supercooling. Based on the current research status of SS-PCMs, this paper summarized the research progress of several important SS-PCMs such as polyol SS-PCMs, polymer SS-PCMs and inorganic salts SS-PCMs in recent years. The classification of SS-PCMs and the performance, heat storage mechanism, advantages and disadvantages of various SS-PCMs were briefly described. Meanwhile, the basic principles of selecting solid-solid phase change materials for application were introduced, and the modification studies on the problems of low thermal conductivity, large supercooling and poor stability of phase change materials were reviewed. The application research of SS-PCMs was also briefly reviewed. Finally, the article pointed out that future research should focus on solving the defects of synthesized SS-PCMs, developing multi-functional SS-PCMs and making breakthroughs in the practical application of SS-PCMs.

Key words: heat storage technology, latent heat storage, solid-solid phase change material, phase change heat storage mechanism, conductivity, supercooling, stability

中图分类号:

TK02

周四丽, 张正国, 方晓明. 固-固相变储热材料的研究进展[J]. 化工进展, 2021, 40(3): 1371-1383.

ZHOU Sili, ZHANG Zhengguo, FANG Xiaoming. Research progress of solid-solid phase change materials for thermal energy storage[J]. Chemical Industry and Engineering Progress, 2021, 40(3): 1371-1383.

图/表 8

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多元醇	固-固转变		固-液转变
多元醇	相变温度/℃	转变热/J·g^-1	相变温度/℃	转变热/J·g^-1
2-氨基-2-甲基-1,3-丙二醇（AMP）	56.96 过冷严重	114.06 —	108.72 102.25	28.02（加热） 25.61（冷却）
新戊二醇（NPG）	44.09 17.51	116.54 81.90	123.05 119.04	28.80（加热） 25.61（冷却）
三羟甲基乙烷（PG）	81.76	172.58	199.63	42.65（加热）
三羟甲基氨基甲烷（TAM）	133.83	270.31	171.72	24.99（加热）
季戊四醇（PE）	185.45 165.19	209.45 180.93	257.07 244.99	33.61（加热） 13.70（冷却）

多元醇	固-固转变		固-液转变
多元醇	相变温度/℃	转变热/J·g^-1	相变温度/℃	转变热/J·g^-1
2-氨基-2-甲基-1,3-丙二醇（AMP）	56.96 过冷严重	114.06 —	108.72 102.25	28.02（加热） 25.61（冷却）
新戊二醇（NPG）	44.09 17.51	116.54 81.90	123.05 119.04	28.80（加热） 25.61（冷却）
三羟甲基乙烷（PG）	81.76	172.58	199.63	42.65（加热）
三羟甲基氨基甲烷（TAM）	133.83	270.31	171.72	24.99（加热）
季戊四醇（PE）	185.45 165.19	209.45 180.93	257.07 244.99	33.61（加热） 13.70（冷却）

PCM	熔化温度/℃	熔化焓/J·g^-1	结晶温度/℃	结晶焓/J·g^-1	升温速率/℃·min^-1	参考文献
纤维素-g-PEG	40.7~60.1	77.6~203.2	25.1~40.6	44.7~203.2	10	[21]
CDA/PEG4000	40	73.6	—	—	5	[22-23]
NCC/PEG4000	47.2	103.8	—	—	5	[24]
纤维素-g-mPEG	40.2~50.4	133.0~175.4	12.2~28.9	97.8~157.7	10	[26]
HB-PUPCM₆₀₀₀	57.5~67.0	91.2~138.2	7.8~33.2	89.4~132.3	10	[27]
HB-PUPCM₆₀₀₀	66.6	124.8	33.1	121.4	10	[51]
HB-PUPCM	56.15~56.99	117.1~146.6	36.61~36.98	88.35~125.6	10/5	[29]
PEG₁₀₀₀₀-MDI-BDO	65.28	138.7	38.58	126.2	10	[30]
PEG₆₀₀₀-MDI-BDO/SA	65.28	152.7	—	—	10	[31]
D-HBPU	59.0	125.0	36.8	120.6	10	[28]
TPUPCM	56.1	137.4	37.5	127.6	—	[32]
PU高聚物-6	57.1	142.5	33.2	137.7	10	[34]
PU高聚物-10	60.8	152.3	34.8	149.7	10	[34]
SPCM	44.3	122.4	37.2	120.3	10	[52]
TPCM	47.8	127.7	38.5	130.2	10	[52]
PEG/MDI/丙三醇	41.8	128.5	38.1	112.3	10	[53]
PEG/MDI/TMP	42.5	119.3	38.3	106.7	10	[53]
PEG₆₀₀₀/PAPI	50.48	111.7	41.38	110.4	10	[54]
BPU	43.4/52.8	86.0/114.9	24.5/28.8	83.1/111.2	10	[35]
NPU	55.8/55.7	136.5/137.5	27.7/33.6	128.0/129.8	10	[35]
Eu-PEG	62.46~72.13	19.83~96.62	24.96~44.89	16.38~83.18	—	[38]
聚苯乙烯-g-PEG₆₀₀₀	44.95~58.04	111.48~179.47	34.36~38.48	99.43~143.6	5	[39]
SMA-g-PEG6000	39.69~45.03	107.04~155.21	23.68~33.56	109.86~142.62	10	[40]
DC-PCM	40.6~71.0	44.3~87.8	7.5~39.2	29.3~107.2	5	[41]
Fe³⁺-PEG	—	97.6	—	92.9	5	[42]
Poly(S-PA-S)	18.72~21.47	26.20~39.78	17.65~18.72	20.02~39.19	5	[43]
SAN-g-PA	24.7~36.1	11.7~24.4	23.9~33.8	11.6~23.7	10	[46]
SMA-g-SA	67.2~67.4	59.3~126.7	62.9~63.8	60.7~125.0	5	[45]
SMA-g-PA	61.0~61.6	41.7~119.8	55.6~57.1	42.4~117.7	5	[45]
SMA-g-MA	53.0~54	35.7~109.7	45.8~47.5	32.4~114.8	5	[45]
SMA-g-LA	42.3~43.7	17.6~84.2	37.3~38.7	13.4~74.8	5	[45]
MBA/PEGA	52.99~57.15	74.13~168.96	30.59~38.27	42.01~145.97	10	[47]
纤维素-g-E2C16	28.2~28.6	21~33	12.9~14.9	18~30	30/10	[48]
CA-g-PAn	17.4~53.2	15~95	5.1~36.7	15~92	10	[50]

PCM	熔化温度/℃	熔化焓/J·g^-1	结晶温度/℃	结晶焓/J·g^-1	升温速率/℃·min^-1	参考文献
纤维素-g-PEG	40.7~60.1	77.6~203.2	25.1~40.6	44.7~203.2	10	[21]
CDA/PEG4000	40	73.6	—	—	5	[22-23]
NCC/PEG4000	47.2	103.8	—	—	5	[24]
纤维素-g-mPEG	40.2~50.4	133.0~175.4	12.2~28.9	97.8~157.7	10	[26]
HB-PUPCM₆₀₀₀	57.5~67.0	91.2~138.2	7.8~33.2	89.4~132.3	10	[27]
HB-PUPCM₆₀₀₀	66.6	124.8	33.1	121.4	10	[51]
HB-PUPCM	56.15~56.99	117.1~146.6	36.61~36.98	88.35~125.6	10/5	[29]
PEG₁₀₀₀₀-MDI-BDO	65.28	138.7	38.58	126.2	10	[30]
PEG₆₀₀₀-MDI-BDO/SA	65.28	152.7	—	—	10	[31]
D-HBPU	59.0	125.0	36.8	120.6	10	[28]
TPUPCM	56.1	137.4	37.5	127.6	—	[32]
PU高聚物-6	57.1	142.5	33.2	137.7	10	[34]
PU高聚物-10	60.8	152.3	34.8	149.7	10	[34]
SPCM	44.3	122.4	37.2	120.3	10	[52]
TPCM	47.8	127.7	38.5	130.2	10	[52]
PEG/MDI/丙三醇	41.8	128.5	38.1	112.3	10	[53]
PEG/MDI/TMP	42.5	119.3	38.3	106.7	10	[53]
PEG₆₀₀₀/PAPI	50.48	111.7	41.38	110.4	10	[54]
BPU	43.4/52.8	86.0/114.9	24.5/28.8	83.1/111.2	10	[35]
NPU	55.8/55.7	136.5/137.5	27.7/33.6	128.0/129.8	10	[35]
Eu-PEG	62.46~72.13	19.83~96.62	24.96~44.89	16.38~83.18	—	[38]
聚苯乙烯-g-PEG₆₀₀₀	44.95~58.04	111.48~179.47	34.36~38.48	99.43~143.6	5	[39]
SMA-g-PEG6000	39.69~45.03	107.04~155.21	23.68~33.56	109.86~142.62	10	[40]
DC-PCM	40.6~71.0	44.3~87.8	7.5~39.2	29.3~107.2	5	[41]
Fe³⁺-PEG	—	97.6	—	92.9	5	[42]
Poly(S-PA-S)	18.72~21.47	26.20~39.78	17.65~18.72	20.02~39.19	5	[43]
SAN-g-PA	24.7~36.1	11.7~24.4	23.9~33.8	11.6~23.7	10	[46]
SMA-g-SA	67.2~67.4	59.3~126.7	62.9~63.8	60.7~125.0	5	[45]
SMA-g-PA	61.0~61.6	41.7~119.8	55.6~57.1	42.4~117.7	5	[45]
SMA-g-MA	53.0~54	35.7~109.7	45.8~47.5	32.4~114.8	5	[45]
SMA-g-LA	42.3~43.7	17.6~84.2	37.3~38.7	13.4~74.8	5	[45]
MBA/PEGA	52.99~57.15	74.13~168.96	30.59~38.27	42.01~145.97	10	[47]
纤维素-g-E2C16	28.2~28.6	21~33	12.9~14.9	18~30	30/10	[48]
CA-g-PAn	17.4~53.2	15~95	5.1~36.7	15~92	10	[50]

PCM	相变温度/℃	相变焓/J·g^-1	熔化温度/℃	熔化焓/J·g^-1	参考文献
(C₁₂H₂₅NH₃)₂ZnCl₄	88.23	105.01	—	—	[6]
(C₁₂H₂₅NH₃)₂CoCl₄	63.85,67.85	33.72,59.30	—	—	[6]
(C₁₂H₂₅NH₃)₂MnCl₄	53.85,55.85	74.31,6.59	—	—	[6]
(C₁₀H₂₁NH₃)₂CuCl₄	33.77	55.13	36.91	7.53	[57]
(C₁₀H₂₁NH₃)₂ZnCl₄	80.14	82.90	162.79	18.14	[57]
(C₁₀H₂₁NH₃)₂CdCl₄	27.0,61.0	34.5,8.25	121.0	13.13	[57]
(C₁₀H₂₁NH₃)₂HgCl₄	36.73	28.02	203.0	50.42	[57]
(C₁₀H₂₁NH₃)₂MnCl₄	32.80	77.44	—	—	[57]
(C₁₀H₂₁NH₃)₂CoCl₄	77.71	74.38	165.0	13.70	[57]
(C₁₀H₂₁NH₃)₂NiCl₄	32.0,58.0	15.2	135.0	65.76	[57]